original_index
int64
2
1.77M
extracted_from_file
stringclasses
489 values
date_of_experiment
timestamp[ns]date
grant_date
timestamp[ns]date
1976-01-01 00:01:00
2016-01-01 00:09:00
is_mapped
bool
1 class
rxn_str
stringlengths
87
6.12k
reactant_000
stringlengths
1
902
reactant_001
stringlengths
1
902
reactant_002
null
agent_000
stringlengths
1
540
agent_001
stringlengths
1
852
agent_002
stringlengths
1
247
agent_003
null
agent_004
null
agent_005
null
agent_006
null
agent_007
null
agent_008
null
agent_009
null
agent_010
null
agent_011
null
agent_012
null
agent_013
null
agent_014
null
agent_015
null
agent_016
null
solvent_000
stringclasses
446 values
solvent_001
stringclasses
405 values
solvent_002
null
solvent_003
null
solvent_004
null
solvent_005
null
solvent_006
null
solvent_007
null
solvent_008
null
solvent_009
null
solvent_010
null
temperature
float64
-230
30.1k
rxn_time
float64
0
2.16k
procedure_details
stringlengths
8
24.5k
product_000
stringlengths
1
484
product_001
null
yield_000
float64
0
90,205,156,600B
yield_001
float64
0
100M
1,719,774
ord_dataset-3f2a531ffbae4b9eb1048afcd7953beb
null
2016-01-01T00:04:00
true
Br[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5](=[O:12])[O:4][C:3]=1[CH:13]([OH:15])[CH3:14].[CH3:16][N:17]([CH3:27])[C:18]1[CH:19]=[C:20](B(O)O)[CH:21]=[CH:22][CH:23]=1.C([O-])([O-])=O.[Cs+].[Cs+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:16][N:17]([CH3:27])[C:18]1[CH:23]=[C:22]([C:2]2[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5](=[O:12])[O:4][C:3]=2[CH:13]([OH:15])[CH3:14])[CH:21]=[CH:20][CH:19]=1
CN(C)c1cccc(B(O)O)c1
CC(O)c1oc(=O)c2ccccc2c1Br
null
c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
O=C([O-])[O-]
[Cs+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was made in a similar way as that of the intermediate B1 using 4-bromo-3-(1-hydroxyethyl)-1H-isochromen-1-one (Intermediate A2, 0.5 g, 1.86 mmol), 3-(dimethylamino)phenylboronic acid (0.46 g, 2.79 mmol), Pd(PPh3)4 (0.11 g, 0.093 mmol) and Cs2CO3 (0.78 g, 2.41 mmol) to afford the title compound (0.2 g, 35%).
CC(O)c1oc(=O)c2ccccc2c1-c1cccc(N(C)C)c1
null
34.8
null
546,191
ord_dataset-d31180f42ced44719fd9e72685c798bf
null
2002-01-01T00:05:00
true
[Cl:1][C:2]1[CH:3]=[C:4]([C:8]2[C:17]3[C:12](=[CH:13][CH:14]=[C:15]([C:18]([C:26]4[CH:27]=[N:28][CH:29]=[CH:30][CH:31]=4)([C:20]4[CH:21]=[N:22][CH:23]=[CH:24][CH:25]=4)[OH:19])[CH:16]=3)[N:11]=[C:10]([O:32]C)[CH:9]=2)[CH:5]=[CH:6][CH:7]=1.Cl>C1COCC1>[Cl:1][C:2]1[CH:3]=[C:4]([C:8]2[C:17]3[C:12](=[CH:13][CH:14]=[C:15]([C:18]([OH:19])([C:20]4[CH:21]=[N:22][CH:23]=[CH:24][CH:25]=4)[C:26]4[CH:27]=[N:28][CH:29]=[CH:30][CH:31]=4)[CH:16]=3)[NH:11][C:10](=[O:32])[CH:9]=2)[CH:5]=[CH:6][CH:7]=1
COc1cc(-c2cccc(Cl)c2)c2cc(C(O)(c3cccnc3)c3cccnc3)ccc2n1
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
null
Following the same procedure as described in example 1F, [4-(3-chloro-phenyl)-2-methoxy-quinolin-6-yl]-di-pyridin-3-yl-methanol (300 mg, 0.66 mmol) was treated with HCl in aqueous THF to yield the title compound (290 mg, 100% yield).
O=c1cc(-c2cccc(Cl)c2)c2cc(C(O)(c3cccnc3)c3cccnc3)ccc2[nH]1
null
99.9
null
742,180
ord_dataset-437aa6654d5044ddaef3346dc4c6e08a
null
2006-01-01T00:11:00
true
[C:1](Cl)(=O)[C:2]([Cl:4])=[O:3].[CH3:7][O:8][C:9]1[CH:17]=[CH:16]C(C(O)=O)=[CH:11][C:10]=1[N+:18]([O-:20])=[O:19]>C1COCC1>[CH3:7][O:8][C:9]1[CH:17]=[CH:16][C:1]([C:2]([Cl:4])=[O:3])=[CH:11][C:10]=1[N+:18]([O-:20])=[O:19]
COc1ccc(C(=O)O)cc1[N+](=O)[O-]
O=C(Cl)C(=O)Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
null
Oxalyl chloride (15.8 ml, 180 mmol) was added dropwise with stirring to a solution of 4-methoxy-3-nitrobenzoic acid (7.00 g, 36.00 mmol) in THF containing 10 μL DMF. After 1 h the solvent was removed under reduced pressure. The product was used directly in the next step.
COc1ccc(C(=O)Cl)cc1[N+](=O)[O-]
null
null
null
1,112,311
ord_dataset-375a420ee9b042918ddca20f02df37d3
null
2011-01-01T00:11:00
true
[Si]([O:8][C@@H:9]([CH3:37])[C@H:10]([C:22]1[O:26][C:25]([C:27]2[CH:32]=[CH:31][C:30]([NH:33][C:34](=[O:36])[CH3:35])=[CH:29][CH:28]=2)=[N:24][N:23]=1)[NH:11][C:12]1[CH:17]=[CH:16][C:15]([C:18]#[N:19])=[C:14]([Cl:20])[C:13]=1[CH3:21])(C(C)(C)C)(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1>[Cl:20][C:14]1[C:13]([CH3:21])=[C:12]([NH:11][C@@H:10]([C:22]2[O:26][C:25]([C:27]3[CH:28]=[CH:29][C:30]([NH:33][C:34](=[O:36])[CH3:35])=[CH:31][CH:32]=3)=[N:24][N:23]=2)[C@@H:9]([OH:8])[CH3:37])[CH:17]=[CH:16][C:15]=1[C:18]#[N:19]
CC(=O)Nc1ccc(-c2nnc([C@H](Nc3ccc(C#N)c(Cl)c3C)[C@H](C)O[Si](C)(C)C(C)(C)C)o2)cc1
null
null
CCCC[N+](CCCC)(CCCC)CCCC
[F-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
11
null
To a pre-cooled (−55° C.) solution of N-(4-(5-((1R,2S)-2-(tert-butyldimethylsilyloxy)-1-(3-chloro-4-cyano-2-methylphenylamino)propyl)-1,3,4-oxadiazol-2-yl)phenyl)acetamide (216 mg, 0.40 mmol) in THF (20 mL) was added TBAF (0.48 mL, 0.48 mmol, 1 M solution in THF) over 5 minutes. Upon complete addition the reaction mixture was allowed to warm to 11° C. over 3 h and quenched with sat. aq. NH4Cl (15 mL). The resulting mixture was partitioned between H2O (25 mL) and EtOAc (40 mL). The aqueous layer was extracted with EtOAc (50 mL). The combined organic extracts were dried (Na2SO4), filtered and concentrated under reduced pressure to provide a colourless oil, which was purified by flash chromatography over silica gel (50-100% EtOAc in hexanes) to provided the title compound as a colourless solid (150 mg, 88%): 1H NMR (400 MHz, d6-acetone, δ in ppm) 9.49 (s 1H), 7.90 (dm, J=9.0 Hz, 2H), 7.80 (dm, J=9.0 Hz, 2H), 7.47 (d, J=8.8 Hz, 1H), 6.85 (d, J=8.6 Hz, 1H), 5.66 (d, J=8.4 Hz, 1H), 5.07 (dd, J=3.7, 8.4 Hz, 1H), 4.84 (br s, 1H), 4.61 (dq, J=3.5, 5.9 Hz, 1H), 2.39 (s, 3H), 2.12 (s, 3H), 1.40 (d, J=6.3 Hz, 3H).
CC(=O)Nc1ccc(-c2nnc([C@H](Nc3ccc(C#N)c(Cl)c3C)[C@H](C)O)o2)cc1
null
88.1
null
31,312
ord_dataset-56c07ce5503b46d1805bdf471f8f1c55
null
1977-01-01T00:10:00
true
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([O:9][CH3:10])[CH:4]=1.C([Li])CCC.CCCCCC.[CH3:22][N:23]1[C:27](=[O:28])[CH2:26][CH2:25][C:24]1=[O:29]>O1CCCC1>[CH3:22][NH:23][C:24](=[O:29])[CH2:25][CH2:26][C:27](=[O:28])[C:4]1[C:3]([O:2][CH3:1])=[CH:8][CH:7]=[CH:6][C:5]=1[O:9][CH3:10]
CN1C(=O)CCC1=O
COc1cccc(OC)c1
null
[Li]CCCC
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
CCCCCC
null
null
null
null
null
null
null
null
null
null
8
A solution of 1,3-dimethoxybenzene (89 ml, 0.064 mole) in dry tetrahydrofuran (480 ml) was added during 10 minutes to a stirred solution of n-butyl lithium in hexane (350 ml, 0.6 mole) under an atmosphere of nitrogen. The stirred mixture was heated under reflux for 90 minutes, then a solution of N-methyl succinimide (77 g, 0.68 mole) in dry tetrahydrofuran was added dropwise. The mixture was heated under reflux for an additional hour and then allowed to stand overnight. The supernatant was decanted and the residue was hydrolysed with 20% aqueous ammonium chloride solution (280 ml) and extracted with chloroform. The washed and dried extract was evaporated and the residue recrystallised from ethyl acetate to give N-methyl 3-(2,6-dimethoxybenzoyl)propionamide (15 g, 10%, m.p. 134°).
CNC(=O)CCC(=O)c1c(OC)cccc1OC
null
93.3
null
623,987
ord_dataset-c9f990dde2dc45d0948ecbe037a0d819
null
2004-01-01T00:01:00
true
[CH3:1][O:2][C:3]1[C:12]([NH:13][C:14](=[O:22])OC2C=CC=CC=2)=[N:11][C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[N:4]=1.[CH3:23][S:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=1[N:31]1[CH2:36][CH2:35][NH:34][CH2:33][CH2:32]1>>[CH3:1][O:2][C:3]1[C:12]([NH:13][C:14]([N:34]2[CH2:33][CH2:32][N:31]([C:26]3[CH:27]=[CH:28][CH:29]=[CH:30][C:25]=3[S:24][CH3:23])[CH2:36][CH2:35]2)=[O:22])=[N:11][C:10]2[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=2)[N:4]=1
COc1nc2ccccc2nc1NC(=O)Oc1ccccc1
CSc1ccccc1N1CCNCC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Phenyl N-(2-methoxyquinoxalin-3-yl)carbamate and 1-(2-methylthiophenyl)piperazine were reacted by the same way with the example 36 to obtain the titled compound.
COc1nc2ccccc2nc1NC(=O)N1CCN(c2ccccc2SC)CC1
null
69.8
null
1,337,693
ord_dataset-08852243bba44cb28769a5833f1515fe
null
2013-01-01T00:09:00
true
[CH2:1]([C:3]1[CH:4]=[C:5]([CH2:8][OH:9])[S:6][CH:7]=1)[CH3:2].[H-].[Na+].Cl[C:13]1[CH:21]2[CH:16]([CH:17]3[O:22][CH:20]2[CH2:19][CH2:18]3)[C:15](=[O:23])[CH:14]=1>C1COCC1>[CH2:1]([C:3]1[CH:4]=[C:5]([CH2:8][O:9][C:13]2[CH:21]3[CH:16]([CH:17]4[O:22][CH:20]3[CH2:19][CH2:18]4)[C:15](=[O:23])[CH:14]=2)[S:6][CH:7]=1)[CH3:2]
CCc1csc(CO)c1
O=C1C=C(Cl)C2C3CCC(O3)C12
null
[H-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
25
3
To a solution of (4-ethyl-thiophen-2-yl)methanol (369 mg, 2 mmol) in THF (10 ml) is added sodium hydride, 60% dispersion in mineral oil, (88 mg, 2.2 mmol) in one portion and the reaction stirred at room temp for 3 hours. The resulting dark yellow solution is then cooled to 0° C., and 5-Chloro-10-oxa-tricyclo[5.2.1.0*2,6*]dec-4-en-3-one (341 mg, 2.4 mmol) is added and the resulting brown solution allowed to warm to ambient over 30 minutes, then stirred at room temp for 17 hours. Crude reaction is purified by flash chromatography to give 5-(4-ethyl-thiophen-2-ylmethoxy)-10-oxa-tricyclo[5.2.1.0*2,6*]dec-4-en-3-one as a white solid (515 mg).
CCc1csc(COC2=CC(=O)C3C4CCC(O4)C23)c1
null
88.7
null
839,368
ord_dataset-074f86301ec5441ab3b52d902ac06949
null
2008-01-01T00:09:00
true
CO[C:3]1[CH:4]=[C:5]([CH:9]([C:15]2[C:24]3[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=3)[CH:18]=[CH:17][CH:16]=2)[CH:10]([C:13]#[N:14])[C:11]#[N:12])[CH:6]=[CH:7][CH:8]=1.[C:25]1(C)C=CC=CC=1[Mg]Br>O1CCCC1>[CH3:25][C:6]1[CH:7]=[CH:8][CH:3]=[CH:4][C:5]=1[CH:9]([C:15]1[C:24]2[C:19](=[CH:20][CH:21]=[CH:22][CH:23]=2)[CH:18]=[CH:17][CH:16]=1)[CH:10]([C:13]#[N:14])[C:11]#[N:12]
Cc1ccccc1[Mg]Br
COc1cccc(C(c2cccc3ccccc23)C(C#N)C#N)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
1.5
A flask was charged with (1-naphthalenylmethylene)-propanedinitrile of Example 3 (408 mg, 2 mmol) and 10 mL anhydrous tetrahydrofuran. To this stirred solution was added, at room temperature, ortho-tolyl magnesium bromide (1.2 mL, 2.4 mmol, 2 M in tetrahydrofuran). The reaction was stirred 1.5 hours, after which it was quenched with 1 N hydrochloric acid and taken up in ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate, brine, dried over magnesium sulfate, filtered, and evaporated to dryness. Following purification on silica (20% ethyl acetate/hexanes) 455 mg product was isolated as an off white foam.
Cc1ccccc1C(c1cccc2ccccc12)C(C#N)C#N
null
null
null
475,791
ord_dataset-d56f0a7ec215495c92e641d9fa932d28
null
2000-01-01T00:09:00
true
[NH2:1][C:2]1[C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[C:10]2[C:4](=[CH:5][CH:6]=[C:7]([CH2:17][C:18]([OH:20])=O)[CH:8]=[CH:9]2)[C:3]=1[C:21]([O:23][CH2:24][CH3:25])=[O:22].C([O:28][P:29]([CH2:34][O:35][NH2:36])([O:31]CC)=[O:30])C>>[NH2:1][C:2]1[C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[C:10]2[C:4](=[CH:5][CH:6]=[C:7]([CH2:17][C:18](=[O:20])[NH:36][O:35][CH2:34][P:29]([OH:31])([OH:30])=[O:28])[CH:8]=[CH:9]2)[C:3]=1[C:21]([O:23][CH2:24][CH3:25])=[O:22]
CCOC(=O)c1c2ccc(CC(=O)O)ccc-2c(C(=O)OCC)c1N
CCOP(=O)(CON)OCC
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
In an analogous manner to that described in Example 26, from diethyl 2-amino-6-carboxymethyl-azulene-1,3-dicarboxylate and phosphonomethoxyamine (L. Maier, Phosphorus, Sulfur, and Silicon 1993, Vol. 76, 119-122) the title compound is obtained as an amorphous powder.
CCOC(=O)c1c2ccc(CC(=O)NOCP(=O)(O)O)ccc-2c(C(=O)OCC)c1N
null
null
null
538,885
ord_dataset-1884c7bf3d544afdb8d17b5d41b90a27
null
2002-01-01T00:03:00
true
[NH2:1][C:2]1[CH:3]=[C:4]([CH:36]=[CH:37][C:38]=1[OH:39])[CH2:5][N:6]1[CH2:11][CH2:10][CH:9]([CH2:12][NH:13][C:14](=[O:35])[CH2:15][NH:16][C:17](=[O:34])[C:18]2[CH:23]=[C:22]([F:24])[C:21]([F:25])=[CH:20][C:19]=2[NH:26]C(OC(C)(C)C)=O)[CH2:8][CH2:7]1.Cl>CO.O1CCOCC1>[NH2:26][C:19]1[CH:20]=[C:21]([F:25])[C:22]([F:24])=[CH:23][C:18]=1[C:17]([NH:16][CH2:15][C:14]([NH:13][CH2:12][CH:9]1[CH2:8][CH2:7][N:6]([CH2:5][C:4]2[CH:36]=[CH:37][C:38]([OH:39])=[C:2]([NH2:1])[CH:3]=2)[CH2:11][CH2:10]1)=[O:35])=[O:34]
CC(C)(C)OC(=O)Nc1cc(F)c(F)cc1C(=O)NCC(=O)NCC1CCN(Cc2ccc(O)c(N)c2)CC1
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
C1COCCO1
null
null
null
null
null
null
null
null
null
25
8
To a solution of 1-(3-amino-4-hydroxybenzyl)-4-[{N-(2-(tert-butoxycarbonylamino)-4,5-difluorobenzoyl)glycyl}aminomethyl]piperidine (20.0 mg, 0.035 mmol) in methanol (1 mL) was added 4 N HCl in dioxane (0.50 mL) and the solution was stirred at room temperature overnight. After the solution was concentrated, the residue was dissolved in methanol, loaded onto Varian™ SCX column, washed with CH3OH (5 mL×2), and eluted off using 2 N NH3 in CH3OH (5 mL). Concentration afforded 4-[{N-(2-amino-4,5-difluorobenzoyl)glycyl}aminomethyl]-1-(3-amino-4-hydroxybenzyl)piperidine (Compound No. 2141) (17.6 mg, quant.). The purity was determined by RPLC/MS (85%); ESI/MS m/e 448.3 (M++H, C22H27F2N5O3).
Nc1cc(CN2CCC(CNC(=O)CNC(=O)c3cc(F)c(F)cc3N)CC2)ccc1O
null
null
null
1,148,026
ord_dataset-b195433d5c354ddfb6cde0d53c41910f
null
2012-01-01T00:04:00
true
[CH2:1]([C:3]1[CH:4]=[C:5]([C:11]2[S:15][C:14]([C:16]3[S:20][C:19]([CH:21]=O)=[C:18]([CH3:23])[CH:17]=3)=[N:13][N:12]=2)[CH:6]=[C:7]([CH3:10])[C:8]=1[OH:9])[CH3:2].[CH3:24][NH:25][CH3:26]>C(O)C>[CH3:24][N:25]([CH2:21][C:19]1[S:20][C:16]([C:14]2[S:15][C:11]([C:5]3[CH:6]=[C:7]([CH3:10])[C:8]([OH:9])=[C:3]([CH2:1][CH3:2])[CH:4]=3)=[N:12][N:13]=2)=[CH:17][C:18]=1[CH3:23])[CH3:26]
CCc1cc(-c2nnc(-c3cc(C)c(C=O)s3)s2)cc(C)c1O
CNC
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
null
null
The title compound (13 mg) is prepared staring from 5-[5-(3-ethyl-4-hydroxy-5-methyl-phenyl)-[1,3,4]thiadiazol-2-yl]-3-methyl-thiophene-2-carbaldehyde (21 mg, 61 μmol) and dimethylamine (33 mg, 244 μmol, as a 33% solution in ethanol) according to Method C; LC-MS: tR=0.56 min; [M+1]+=374.07; 1H NMR (D6-DMSO): δ1.18 (t, J=7.3 Hz, 3H), 2.20 (s, 3H), 2.24 (s, 6H), 2.26 (s, 3H), 2.67 (q, J=7.3 Hz, 2H), 3.57 (s, 2H), 7.47 (s, 1H), 7.56 (s, 2H).
CCc1cc(-c2nnc(-c3cc(C)c(CN(C)C)s3)s2)cc(C)c1O
null
null
null
1,120,342
ord_dataset-4226e9b4f9f845db967ed997270dcafc
null
2011-01-01T00:12:00
true
[CH2:1]1[C:6]2([CH2:11][C:10](=[O:12])[CH2:9][C:8](=[O:13])[CH2:7]2)[CH2:5][CH2:4][O:3][CH2:2]1.C1(C)C=CC=CC=1.C([O-])(=O)C.C([O-])(=O)C.C([O-])(=O)C.[CH3:33][C:34]1[C:39]([Pb+3])=[C:38]([CH3:41])[CH:37]=[C:36]([C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=2)[CH:35]=1.Cl>CN(C)C1C=CN=CC=1.C(Cl)(Cl)Cl>[CH3:33][C:34]1[CH:35]=[C:36]([C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][CH:43]=2)[CH:37]=[C:38]([CH3:41])[C:39]=1[CH:9]1[C:10](=[O:12])[CH2:11][C:6]2([CH2:5][CH2:4][O:3][CH2:2][CH2:1]2)[CH2:7][C:8]1=[O:13]
O=C1CC(=O)CC2(CCOCC2)C1
Cc1cc(-c2ccccc2)cc(C)c1[Pb+3]
null
CC(=O)[O-]
CN(C)c1ccncc1
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)Cl
Cc1ccccc1
null
null
null
null
null
null
null
null
null
25
null
To a mixture of 3-oxaspiro[5.5]undecane-8,10-dione (0.182 g, 1 mmol) and 4-dimethylamino-pyridine (0.61 g; 5 mmol) is added dry chloroform (4 ml), and the mixture is stirred under an atmosphere of nitrogen at room temperature until the solid dissolves. To this solution is then added dry toluene (2 ml), and then a solution of 3,5-dimethylbiphen-4-yllead triacetate (1.2 mmol) in chloroform is added. The reaction mixture is heated under reflux for 1 hour, then cooled to room temperature, acidified to pH=1 with 2N aqueous hydrochloric acid, filtered and the filtrate is extracted with dichloromethane (2×40 ml). The organic extracts are combined, dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated in vacuo. The residue is purified by column chromatography over silica gel to give 9-(3,5-dimethylbiphenyl-4-yl)-3-oxa-spiro[5.5]undecane-8,10-dione.
Cc1cc(-c2ccccc2)cc(C)c1C1C(=O)CC2(CCOCC2)CC1=O
null
null
null
1,536,758
ord_dataset-8d5c200bca27407ab9febe7598e16458
null
2015-01-01T00:01:00
true
[CH2:1]([O:3][C:4]([C:6]1[CH:7]=[N:8][N:9]([C:11](=[N:18][C:19]2[CH:24]=[CH:23][C:22]([Br:25])=[CH:21][CH:20]=2)[NH:12][C:13](OCC)=[O:14])[CH:10]=1)=[O:5])[CH3:2].ClCCCl>[Ti](Cl)(Cl)(Cl)Cl.C(Cl)Cl>[CH2:1]([O:3][C:4]([C:6]1[CH:7]=[N:8][N:9]([C:11]2[NH:12][C:13](=[O:14])[C:24]3[C:19](=[CH:20][CH:21]=[C:22]([Br:25])[CH:23]=3)[N:18]=2)[CH:10]=1)=[O:5])[CH3:2]
CCOC(=O)NC(=Nc1ccc(Br)cc1)n1cc(C(=O)OCC)cn1
null
null
Cl[Ti](Cl)(Cl)Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
ClCCCl
null
null
null
null
null
null
null
null
null
100
2
Titanium (IV) chloride (2.47 mL, 22.5 mmol) was carefully added to a solution of 1-[(4-bromo-phenylimino)-ethoxycarbonylamino-methyl]-1H-pyrazole-4-carboxylic acid ethyl ester (1.84 g, 4.50 mmol) and DCE (45 mL), and the resulting solution was heated to 100° C. for 15 h. The reaction mixture was cooled to room temperature and poured into ice water (50 mL) and DCM (100 mL) was added. The biphasic mixture was stirred for 2 h, and the layers were separated. The aqueous layer was further extracted with DCM (2×50 mL). The combined organic layers were washed with brine (50 mL), dried (MgSO4), and concentrated. The residue was triturated from EtOH to yield the titled compound (1.05 g, 64% yield). MS (ESI/Cl): mass calcd. for C14H11BrN4O3, 362.0; m/z found, 363.0 [M+H]+. 1H NMR (600 MHz, DMSO-d6): 13.15 (s, 1H), 9.01 (d, J=0.5 Hz, 1H), 8.33 (s, 1H), 8.20 (d, J=2.3 Hz, 1H), 7.99 (dd, J=8.7, 2.4 Hz, 1H), 7.66 (d, J=8.8 Hz, 1H), 4.30 (q, J=7.1 Hz, 2H), 1.32 (t, J=7.1 Hz, 3H).
CCOC(=O)c1cnn(-c2nc3ccc(Br)cc3c(=O)[nH]2)c1
null
64.2
null
1,764,325
ord_dataset-0b32b90cc77b4a3db47ad263e0bbc1a8
null
2016-01-01T00:09:00
true
[NH:1]1[CH:5]=[C:4]([C:6]2[N:11]=[CH:10][C:9]3[CH:12]=[N:13][N:14]([C:15]4[N:20]=[C:19]([N:21]5[CH2:27][CH2:26][CH2:25][N:24](C(OC(C)(C)C)=O)[CH2:23][CH2:22]5)[CH:18]=[CH:17][CH:16]=4)[C:8]=3[CH:7]=2)[CH:3]=[N:2]1.Br[CH:36]1[CH2:39][CH2:38][CH2:37]1>>[N:21]1([C:19]2[N:20]=[C:15]([N:14]3[C:8]4[CH:7]=[C:6]([C:4]5[CH:5]=[N:1][N:2]([CH:36]6[CH2:39][CH2:38][CH2:37]6)[CH:3]=5)[N:11]=[CH:10][C:9]=4[CH:12]=[N:13]3)[CH:16]=[CH:17][CH:18]=2)[CH2:27][CH2:26][CH2:25][NH:24][CH2:23][CH2:22]1
CC(C)(C)OC(=O)N1CCCN(c2cccc(-n3ncc4cnc(-c5cn[nH]c5)cc43)n2)CC1
BrC1CCC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Following the procedures as described in Example 61 and starting with tert-butyl 4-(6-(6-(1H-pyrazol-4-yl)-1H-pyrazolo[4,3-c]pyridin-1-yl)pyridin-2-yl)-1,4-diazepane-1-carboxylate and bromocyclobutane, 147 was obtained as a yellow solid (40 mg, 35%) over two steps. 1H-NMR (500 MHz, CD3OD) δ (ppm): 9.02 (s, 1H), 8.66 (s, 1H), 8.34 (s, 1H), 8.18 (s, 1H), 7.95 (s, 1H), 7.66-7.69 (m, 1H), 7.25 (d, J=7.5 Hz, 1H), 6.59 (d, J=8.5 Hz, 1H), 4.91-4.96 (m, 1H), 3.90-3.95 (m, 4H), 3.20-3.22 (m, 2H), 3.00-3.02 (m, 2H), 2.52-2.63 (m, 4H), 2.08-2.13 (m, 2H), 1.92-1.99 (m, 2H); MS (ESI) m/z: 415 [M+H]+.
c1cc(N2CCCNCC2)nc(-n2ncc3cnc(-c4cnn(C5CCC5)c4)cc32)c1
null
35
null
1,208,361
ord_dataset-fb72428f30234761b4216139dc228d0c
null
2012-01-01T00:09:00
true
[CH:1]1([C:4]([NH:6][C:7]2[N:8]=[C:9]3[CH:14]=[CH:13][C:12]([O:15][C:16]4[CH:26]=[CH:25][CH:24]=[CH:23][C:17]=4[C:18]([O:20]CC)=[O:19])=[N:11][N:10]3[CH:27]=2)=[O:5])[CH2:3][CH2:2]1.[OH-].[Na+].Cl.C(OCC)(=O)C>O1CCCC1>[CH:1]1([C:4]([NH:6][C:7]2[N:8]=[C:9]3[CH:14]=[CH:13][C:12]([O:15][C:16]4[CH:26]=[CH:25][CH:24]=[CH:23][C:17]=4[C:18]([OH:20])=[O:19])=[N:11][N:10]3[CH:27]=2)=[O:5])[CH2:3][CH2:2]1
CCOC(=O)c1ccccc1Oc1ccc2nc(NC(=O)C3CC3)cn2n1
null
null
Cl
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
C1CCOC1
null
null
null
null
null
null
null
null
null
25
3
To a solution of ethyl 2-({2-[(cyclopropylcarbonyl)amino]imidazo[1,2-b]pyridazin-6-yl}oxy)benzoate (200 mg, 0.54 mmol) in tetrahydrofuran (10 mL) was added 4N aqueous sodium hydroxide solution (1.5 mL), and the mixture was stirred at room temperature for 3 hr. 6N Hydrochloric acid (1.5 mL) and ethyl acetate were added to the reaction mixture, and the aqueous layer was extracted with ethyl acetate (×4). Combined organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and filtrated. The filtrate was concentrated under reduced pressure, and the residue was washed with ethyl acetate/hexane to give the title compound (130 mg, 73%) as a white solid.
O=C(O)c1ccccc1Oc1ccc2nc(NC(=O)C3CC3)cn2n1
null
71.2
null
282,818
ord_dataset-769fac6048e548eca2d49e48f972884b
null
1994-01-01T00:01:00
true
[CH2:1]([C:5]1[NH:6][C:7]([C:15]#[N:16])=[C:8]([N:10]2[CH:14]=[CH:13][CH:12]=[CH:11]2)[N:9]=1)[CH2:2][CH2:3][CH3:4].CC(C)([O-])C.[K+].C1(C(C2C=CC=CC=2)(C2C=CC=CC=2)[N:30]2[C:34]([C:35]3[CH:40]=[CH:39][CH:38]=[CH:37][C:36]=3[C:41]3[CH:46]=[CH:45][C:44]([CH2:47]Br)=[CH:43][CH:42]=3)=[N:33][N:32]=[N:31]2)C=CC=CC=1>O1CCCC1>[CH2:1]([C:5]1[N:6]([CH2:47][C:44]2[CH:45]=[CH:46][C:41]([C:36]3[CH:37]=[CH:38][CH:39]=[CH:40][C:35]=3[C:34]3[NH:30][N:31]=[N:32][N:33]=3)=[CH:42][CH:43]=2)[C:7]([C:15]#[N:16])=[C:8]([N:10]2[CH:11]=[CH:12][CH:13]=[CH:14]2)[N:9]=1)[CH2:2][CH2:3][CH3:4]
BrCc1ccc(-c2ccccc2-c2nnnn2C(c2ccccc2)(c2ccccc2)c2ccccc2)cc1
CCCCc1nc(-n2cccc2)c(C#N)[nH]1
null
CC(C)(C)[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
0.08
A solution of 2-butyl-5-cyano-4-(1H-pyrrol-1-yl)imidazole (Example 8, 1.7 g) in anhydrous tetrahydrofuran (20 mL) was treated with a solution of potassium tert-butoxide (0.97 g) in anhydrous tetrahydrofuran (20 mL) at room temperature. The mixture was stirred for 5 minutes then a solution of N-triphenylmethyl-5-[4'-(bromomethyl)biphenyl-2-yl]tetrazole (Example 12, 6.0 g) in anhydrous tetrahydrofuran (20 mL) was added. The reaction was stirred at room temperature under nitrogen atmosphere for 18 hours. The resulting suspension was filtered and the filtrate was evaporated. The residue was purified by flash chromatography on silica gel, eluting with chloroform hexane (90:10) to give the title compound in its triphenylmethyl-protected form. The triphenylmethyl protecting group was removed by refluxing in methanol for 24 hours. Evaporation gave a residue that was purified by chromatography on silica gel, eluting with a gradient of ethyl acetate-hexane (50:50) to ethyl acetate. Evaporation of solvents gave a gum that was redissolved in dichloromethane and evaporated to give the title compound as a solid foam. MS (FAB, thioglycerol) 470 (m+Na-1), 448 (m).
CCCCc1nc(-n2cccc2)c(C#N)n1Cc1ccc(-c2ccccc2-c2nnn[nH]2)cc1
null
null
null
205,505
ord_dataset-72fffaae67c8473fb9d951cb1b026646
null
1990-01-01T00:03:00
true
[OH:1][C:2]1[CH:9]=[CH:8][C:7]([C:10]([CH3:13])([CH3:12])[CH3:11])=[C:6]([Cl:14])[C:3]=1[CH:4]=[O:5].[Br:15]N1C(=O)CCC1=O.O>C(Cl)Cl>[OH:1][C:2]1[C:9]([Br:15])=[CH:8][C:7]([C:10]([CH3:11])([CH3:13])[CH3:12])=[C:6]([Cl:14])[C:3]=1[CH:4]=[O:5]
CC(C)(C)c1ccc(O)c(C=O)c1Cl
O=C1CCC(=O)N1Br
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
ClCCl
null
null
null
null
null
null
null
null
null
null
null
A solution of 1.97 g (9.26 mmol) of 2-hydroxy-5-(1,1-dimethylethyl)-6-chlorobenzaldehyde and 1.98 g (11.1 mmol) of N-bromosuccinimide in 30 ml of methylene chloride was stirred for 2 hours. Water (50 ml) was added. The organic phase was dried and evaporated. The residue was chromatographed on 150 g of silica gel eluted with 1:99 (v/v) ether:hexane. There was obtained 2.69 g (9.22 mmol, 99%) of 2-hydroxy-3-bromo-5-(1,1-dimethylethyl)-6-chlorobenzaldehyde as a white solid after recrystallization from hexane; mp 103°-105° C.
CC(C)(C)c1cc(Br)c(O)c(C=O)c1Cl
null
99.6
null
1,023,881
ord_dataset-136cfada6ce247b4919085a57363459e
null
2011-01-01T00:01:00
true
[CH2:1]([O:3][C:4]([C:6]1([CH2:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:11][CH2:10][NH:9][CH2:8][CH2:7]1)=[O:5])[CH3:2].[N:19]([O-])=[O:20].[Na+].C(O)(=O)C.C(=O)([O-])O.[Na+]>O>[CH2:1]([O:3][C:4]([C:6]1([CH2:12][C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)[CH2:7][CH2:8][N:9]([N:19]=[O:20])[CH2:10][CH2:11]1)=[O:5])[CH3:2]
O=N[O-]
CCOC(=O)C1(Cc2ccccc2)CCNCC1
null
O=C([O-])O
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CC(=O)O
null
null
null
null
null
null
null
null
null
25
8
To a solution of 4-ethoxycarbonyl-4-benzylpiperidine (495 mg) in water (5 mL) was added sodium nitrite (276 mg) and acetic acid (201 μL) and the mixture was stirred at room temperature overnight. To the reaction mixture was added an aqueous saturated sodium hydrogencarbonate solution and the mixture was stirred and extracted with chloroform. The extract was concentrated in vacuo and the resultant crude product was purified by column chromatography on silica gel (solvent: hexane/ethyl acetate=85/15 to 80/20) and dried in vacuo to give 4-ethoxycarbonyl-4-benzyl-1-nitrosopiperidine (565 mg, yield: 100%) as a colorless solid. To a solution of the product (565 mg) in methanol (3 mL) was added zinc powder (654 mg) and then added acetic acid (3 mL) under ice-cooling and the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered and the filtrate was concentrated in vacuo. To the residue was added an aqueous saturated sodium hydrogencarbonate solution and chloroform and the mixture was stirred and extracted with chloroform. The extract was dried over magnesium sulfate and filtered. The filtrate was concentrated in vacuo to give 1-amino-4-benzyl-4-ethoxycarbonylpiperidine (508 mg, yield: 97%) as a colorless viscidity.
CCOC(=O)C1(Cc2ccccc2)CCN(N=O)CC1
null
102.2
null
218,343
ord_dataset-640d007e35e243a286c8b7dd2b77ac1b
null
1990-01-01T00:11:00
true
CS(C)=O.C(=O)([O-])[O-].[K+].[K+].[I-].[K+].[CH:13](Br)([CH2:15][CH3:16])[CH3:14].[OH:18][C:19]1[C:28]([OH:29])=[C:27]2[C:22]([C:23](=[O:32])[CH2:24][C:25]([CH3:31])([CH3:30])[O:26]2)=[CH:21][CH:20]=1>COCCOCCOC>[CH:13]([O:18][C:19]1[C:28]([OH:29])=[C:27]2[C:22]([C:23](=[O:32])[CH2:24][C:25]([CH3:30])([CH3:31])[O:26]2)=[CH:21][CH:20]=1)([CH2:15][CH3:16])[CH3:14]
CC1(C)CC(=O)c2ccc(O)c(O)c2O1
CCC(C)Br
null
O=C([O-])[O-]
[I-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
COCCOCCOC
CS(C)=O
null
null
null
null
null
null
null
null
null
100
2
In 80 ml of dimethyl sulfoxide 4.2 g (20 millimoles) of 7.8-dihydroxy-2,2-dimethyl-4-chromanone are dissolved, whereupon 10 ml of diethylene glycol dimethylether, 4.1 g (30 millimoles) of potassium carbonate, 0.5 g of potassium iodide and 3.3 (2.6 ml, 24 millimoles) of sec. butyl bromide are added. The reaction mixture is heated at 100° C. for 10 hours, poured onto 200 ml of crushed ice and extracted with 100 ml of carbon tetrachloride. To the aqueous phase 20 ml of 10% sodium hydroxide solution are added, the mixture is cooled to 0° C., acidified with concentrated hydrochloric acid and stirred at 0° C. for 2 hours. The product is filtered, washed twice with 20 ml of water, dried and crystallized from 20% ethanol. Thus 4.4. g of the desired compound are obtained, yield 83%, mp.: 108°-110° C.
CCC(C)Oc1ccc2c(c1O)OC(C)(C)CC2=O
null
83
null
856,058
ord_dataset-faa0236be76c4501841c954527cd1b6c
null
2008-01-01T00:12:00
true
[CH3:1][N:2]1[CH:6]=[CH:5][C:4]([C:7]([OH:9])=O)=[N:3]1.Cl.Cl.[F:12][C:13]1[CH:14]=[C:15]2[C:20](=[CH:21][C:22]=1[F:23])[N:19]=[C:18]([NH:24][CH2:25][CH2:26][NH:27][CH3:28])[CH:17]=[N:16]2>>[F:12][C:13]1[CH:14]=[C:15]2[C:20](=[CH:21][C:22]=1[F:23])[N:19]=[C:18]([NH:24][CH2:25][CH2:26][N:27]([CH3:28])[C:7]([C:4]1[C:5]([C:20]3[CH:15]=[CH:14][C:13]([F:12])=[CH:22][CH:21]=3)=[CH:6][N:2]([CH3:1])[N:3]=1)=[O:9])[CH:17]=[N:16]2
Cn1ccc(C(=O)O)n1
CNCCNc1cnc2cc(F)c(F)cc2n1
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared from 4-4-fluoro-phenyl)-1-methyl-1H-pyrazole-3-carboxylic acid (46 mg, 0.21 mmol) and N-(6,7-difluoro-quinoxalin-2-yl)-N′-methyl-ethane-1,2-diamine.dihydrochloride, D2 (65 mg, 0.21 mmol) according to the procedure described for Example 1, as a yellow solid (65 mg, 71%).
CN(CCNc1cnc2cc(F)c(F)cc2n1)C(=O)c1nn(C)cc1-c1ccc(F)cc1
null
null
null
1,176,331
ord_dataset-0f9d2dbe929a45c3892ae75e81e99443
null
2012-01-01T00:06:00
true
Cl[C:2]1[CH:3]=[CH:4][C:5]2[N:6]([C:8]([NH2:11])=[N:9][N:10]=2)[N:7]=1.[O-:12][CH2:13][CH3:14].[Na+].O>C(O)C>[CH2:13]([O:12][C:2]1[CH:3]=[CH:4][C:5]2[N:6]([C:8]([NH2:11])=[N:9][N:10]=2)[N:7]=1)[CH3:14]
CC[O-]
Nc1nnc2ccc(Cl)nn12
null
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
O
null
null
null
null
null
null
null
null
null
55
2
6-Chloro-[1,2,4]triazolo[4,3-b]pyridazin-3-ylamine (W2.001a, 616 mg) was dissolved in absolute ethanol (40 ml) and admixed with portions of solid sodium ethoxide (990 mg). After stirring at 55° C. for 2 h, water was added and the aqueous phase was extracted three times with dichloromethane. The combined extracts were dried over sodium sulfate, filtered and concentrated. 709 mg of crude product of the desired compound were obtained in sufficient purity.
CCOc1ccc2nnc(N)n2n1
null
108.9
null
1,574,571
ord_dataset-9741bb5fd93044078df2a45f45733054
null
2015-01-01T00:04:00
true
[CH3:1][S:2]([N:5]1[CH2:10][CH:9]=[C:8]([C:11]2[CH:12]=[C:13]3[CH:19]=[C:18]([CH:20]4[CH2:25][CH2:24][NH:23][CH2:22][CH2:21]4)[O:17][C:14]3=[CH:15][N:16]=2)[CH2:7][CH2:6]1)(=[O:4])=[O:3].Cl[C:27]1[N:32]=[CH:31][C:30]([Cl:33])=[CH:29][N:28]=1>>[Cl:33][C:30]1[CH:29]=[N:28][C:27]([N:23]2[CH2:24][CH2:25][CH:20]([C:18]3[O:17][C:14]4=[CH:15][N:16]=[C:11]([C:8]5[CH2:9][CH2:10][N:5]([S:2]([CH3:1])(=[O:3])=[O:4])[CH2:6][CH:7]=5)[CH:12]=[C:13]4[CH:19]=3)[CH2:21][CH2:22]2)=[N:32][CH:31]=1
Clc1cnc(Cl)nc1
CS(=O)(=O)N1CC=C(c2cc3cc(C4CCNCC4)oc3cn2)CC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound is prepared from 5-(1-methanesulfonyl-1,2,3,6-tetrahydro-pyridin-4-yl)-2-piperidin-4-yl-furo[2,3-c]pyridine and 2,5-dichloropyrimidine following a procedure analogous to that described for Example 23. LC (method 1): tR=1.07 min; Mass spectrum (ESI+): m/z=474/476 (Cl) [M+H]+.
CS(=O)(=O)N1CC=C(c2cc3cc(C4CCN(c5ncc(Cl)cn5)CC4)oc3cn2)CC1
null
null
null
1,749,904
ord_dataset-60a3e71da3174666a50a61dcfa611a9f
null
2016-01-01T00:07:00
true
C(OC([NH:8][CH2:9][C:10]([O:12][CH2:13][N:14]1[C:18]2=[N:19][CH:20]=[C:21]([C:23]3[CH:28]=[CH:27][C:26]([Cl:29])=[CH:25][CH:24]=3)[CH:22]=[C:17]2[C:16]([C:30](=[O:46])[C:31]2[C:36]([F:37])=[CH:35][CH:34]=[C:33]([NH:38][S:39]([CH2:42][CH2:43][CH3:44])(=[O:41])=[O:40])[C:32]=2[F:45])=[CH:15]1)=[O:11])=O)(C)(C)C.Cl>CCOC(C)=O>[ClH:29].[NH2:8][CH2:9][C:10]([O:12][CH2:13][N:14]1[C:18]2=[N:19][CH:20]=[C:21]([C:23]3[CH:28]=[CH:27][C:26]([Cl:29])=[CH:25][CH:24]=3)[CH:22]=[C:17]2[C:16]([C:30](=[O:46])[C:31]2[C:36]([F:37])=[CH:35][CH:34]=[C:33]([NH:38][S:39]([CH2:42][CH2:43][CH3:44])(=[O:40])=[O:41])[C:32]=2[F:45])=[CH:15]1)=[O:11]
CCCS(=O)(=O)Nc1ccc(F)c(C(=O)c2cn(COC(=O)CNC(=O)OC(C)(C)C)c3ncc(-c4ccc(Cl)cc4)cc23)c1F
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared according to the procedure as described in Example 17 Step 3 using (5-(4-chlorophenyl)-3-(2,6-difluoro-3-(propylsulfonamido)benzoyl)-1H-pyrrolo[2,3-b]pyridin-1-yl)methyl 2-((tert-butoxycarbonyl)amino)acetate (46 mg, 0.07 mmol) and a saturated solution of HCl in EtOAc (2 mL). The title compound was obtained as a white solid (36 mg, 83.7%). The title compound was characterized by LC-MS and 1H NMR as shown below:
CCCS(=O)(=O)Nc1ccc(F)c(C(=O)c2cn(COC(=O)CN)c3ncc(-c4ccc(Cl)cc4)cc23)c1F
null
null
null
305,003
ord_dataset-180e296d6d6245638d4d22a59120ea01
null
1995-01-01T00:02:00
true
[CH2:1]([C:5]1[N:9]([CH2:10][C:11]2[CH:16]=[CH:15][C:14]([C:17]3[C:18]([C:23]#[N:24])=[N:19][CH:20]=[N:21][CH:22]=3)=[CH:13][CH:12]=2)[C:8]2[C:25]([C:29]([O:31][CH3:32])=[O:30])=[CH:26][CH:27]=[CH:28][C:7]=2[N:6]=1)[CH2:2][CH2:3][CH3:4].C[Sn]([N:37]=[N+:38]=[N-:39])(C)C>C1(C)C=CC=CC=1>[CH2:1]([C:5]1[N:9]([CH2:10][C:11]2[CH:16]=[CH:15][C:14]([C:17]3[C:18]([C:23]4[NH:39][N:38]=[N:37][N:24]=4)=[N:19][CH:20]=[N:21][CH:22]=3)=[CH:13][CH:12]=2)[C:8]2[C:25]([C:29]([O:31][CH3:32])=[O:30])=[CH:26][CH:27]=[CH:28][C:7]=2[N:6]=1)[CH2:2][CH2:3][CH3:4]
C[Sn](C)(C)N=[N+]=[N-]
CCCCc1nc2cccc(C(=O)OC)c2n1Cc1ccc(-c2cncnc2C#N)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
A solution of methyl 2-butyl-1-[p-(4-cyanopyrimidin-5-yl)benzyl]benzimidazole-7-carboxylate (0.18 g, 0.4 mmol) and trimethyltin azide (0.27 g, 1.3 mmol) in toluene (5 ml) was heated under reflux for 28 hours. After removal of the solvent by evaporation, the residue was purified by column chromatography on silica gel. Recrystallization from ethyl acetate-isopropyl ether afforded colorless powders (40 mg, 20%), m.p. 215°-220° C.
CCCCc1nc2cccc(C(=O)OC)c2n1Cc1ccc(-c2cncnc2-c2nnn[nH]2)cc1
null
null
null
1,447,833
ord_dataset-a86112d52cd54525a5e36d41f18aced2
null
2014-01-01T00:07:00
true
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C@H:8]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=2[CH3:25])[CH2:9][C:10]([C:12]2[CH:13]=[CH:14][C:15](=[O:18])[NH:16][CH:17]=2)=[O:11])=[CH:4][CH:3]=1.IC.[C:28](=O)([O-])[O-].[K+].[K+]>>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C@H:8]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][C:20]=2[CH3:25])[CH2:9][C:10]([C:12]2[CH:13]=[CH:14][C:15](=[O:18])[N:16]([CH3:28])[CH:17]=2)=[O:11])=[CH:6][CH:7]=1
O=C([O-])[O-]
Cc1ccccc1[C@H](CC(=O)c1ccc(=O)[nH]c1)c1ccc(Br)cc1
null
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CI
null
null
null
null
null
null
null
null
null
null
null
null
In analogy to example 161, step 1, 5-[(R)-3-(4-bromo-phenyl)-3-o-tolyl-propionyl]-1H-pyridin-2-one was reacted with iodomethane in the presence of potassium carbonate to give the title compound as a colorless solid, MS (ESI+): m/z=410.2 [M+H]+.
Cc1ccccc1[C@H](CC(=O)c1ccc(=O)n(C)c1)c1ccc(Br)cc1
null
null
null
1,629,968
ord_dataset-f0794d5ded7a4d3fab45cc3d7a89ee3d
null
2015-01-01T00:09:00
true
[C:1]([O:5][C:6]([NH:8][C@@H:9]1[C@H:14]([OH:15])[CH2:13][CH2:12][N:11](C(OCC2C=CC=CC=2)=O)[CH2:10]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]>C(O)C.[Pd]>[C:1]([O:5][C:6](=[O:7])[NH:8][C@@H:9]1[C@H:14]([OH:15])[CH2:13][CH2:12][NH:11][CH2:10]1)([CH3:4])([CH3:2])[CH3:3]
CC(C)(C)OC(=O)N[C@H]1CN(C(=O)OCc2ccccc2)CC[C@H]1O
null
null
[Pd]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
null
8
A solution of (3S,4R)-benzyl 3-((tert-butoxycarbonyl)amino)-4-hydroxypiperidine-1-carboxylate (1.94 g, 5.54 mmol) in ethanol (48 mL) was added to a hydrogenation flask containing 10% Pd/C (0.059 g, 0.554 mmol) that had been evacuated and back-filled with N2 (×3). The flask was again evacuated and then back-filled with H2 (×3). Enough H2 to allow complete reaction was then introduced to a burette and the system closed and the flask allowed to stir under a H2 atmosphere overnight. The reaction mixture was filtered through Celite and washed with EtOH (2×20 mL) and ethyl acetate (2×20 mL). The combined filtrate was concentrated in vacuo to afford the product as a cream oily solid—tert-butyl((3S,4R)-4-hydroxypiperidin-3-yl)carbamate (1.13 g, 5.22 mmol, 94% yield).
CC(C)(C)OC(=O)N[C@H]1CNCC[C@H]1O
null
94.2
null
1,610,445
ord_dataset-9cecb3a8d3b9494191b28dcefea66af2
null
2015-01-01T00:07:00
true
[CH3:1][O:2][C:3]1[CH:8]=[C:7]([CH3:9])[NH:6][C:5](=[O:10])[C:4]=1[CH2:11][NH:12][C:13]([C:15]1[C:23]2[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=2)[N:17]([CH:24]([CH:26]2[CH2:31][CH2:30][CH2:29][NH:28][CH2:27]2)[CH3:25])[C:16]=1[CH3:32])=[O:14].C(N(CC)CC)C.[CH3:40][S:41](Cl)(=[O:43])=[O:42]>ClCCl>[CH3:1][O:2][C:3]1[CH:8]=[C:7]([CH3:9])[NH:6][C:5](=[O:10])[C:4]=1[CH2:11][NH:12][C:13]([C:15]1[C:23]2[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=2)[N:17]([CH:24]([CH:26]2[CH2:31][CH2:30][CH2:29][N:28]([S:41]([CH3:40])(=[O:43])=[O:42])[CH2:27]2)[CH3:25])[C:16]=1[CH3:32])=[O:14]
COc1cc(C)[nH]c(=O)c1CNC(=O)c1c(C)n(C(C)C2CCCNC2)c2ccccc12
CS(=O)(=O)Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(CC)CC
ClCCl
null
null
null
null
null
null
null
null
null
25
12
To a solution of N-((4-methoxy-6-methyl-2-oxo-1,2-dihydropyridin-3-yl)methyl)-2-methyl-1-(1-(piperidin-3-yl)ethyl)-1H-indole-3-carboxamide (20 mg, 45.81 mol) in dichloromethane (3 mL) was added triethylamine (9.27 mg, 91.63 μmol) and methanesulfonyl chloride (7.87 mg, 68.72 μmol). The mixture was stirred at room temperature for 12 hours. The mixture was evaporated and purified by preparative-HPLC (Instrument: Gilson GX281 Column: Phenomenex Gemini C18 250*21.2 mm Mobile phase A: water with 0.01 mol/1NH4HCO3; Mobile phase B: MeCN Column temperature: 30° C. Gradient: 23-53% B 10 min) to afford the title compound (7 mg, yield: 29.69%). LRMS (M+H+) m/z: calc'd 515.22. found 515.2. 1H NMR (400 MHz, METHANOL-d4) δ 0.94-1.12 (m, 2 H) 1.39 (br. S., 2 H) 1.57-1.70 (m, 4 H) 2.33 (s, 3 H) 2.63 (s, 3 H) 2.83 (d, J=9.54 Hz, 2 H) 2.88 (s, 3 H) 3.48 (br. S., 1 H) 3.79-3.87 (m, 1 H) 3.95 (s, 3 H) 4.38 (br. S., 1 H) 4.54 (s, 2 H) 6.28 (s, 1 H) 7.07-7.17 (m, 2 H) 7.58 (d, J=8.03 Hz, 1 H) 7.72 (d, J=7.53 Hz, 1 H).
COc1cc(C)[nH]c(=O)c1CNC(=O)c1c(C)n(C(C)C2CCCN(S(C)(=O)=O)C2)c2ccccc12
null
19.8
null
1,626,927
ord_dataset-f0794d5ded7a4d3fab45cc3d7a89ee3d
null
2015-01-01T00:09:00
true
[CH2:1]([NH2:4])[C:2]#[CH:3].[CH2:5]1[C:14]2[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=2)[CH2:8][CH2:7][C:6]1=O>C(O)C>[CH:3]1[C:10]2[C:9]3[CH:8]=[CH:7][CH:6]=[CH:5][C:14]=3[CH2:13][CH2:12][C:11]=2[N:4]=[CH:1][CH:2]=1
O=C1CCc2ccccc2C1
C#CCN
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
25
0.25
Propargylamine (5 mL) is added to a flask charged with a stir bar, 2-tetralone (10.00 g), NaAuCl4*2H2O (0.65 g), and ethanol (50 mL) (caution: a very exothermic reaction may evolve afterwards→keep an ice bath at hand). The resulting mixture is stirred at room temperature for 15 min and then at reflux temperature for 1 h. After cooling the mixture to room temperature, the solvent is evaporated and the residue is chromatographed on silica gel (cyclohexane/ethyl acetate 60:40) to afford the title compound as an oil. Yield: 6.78 g (56% of theory); LC (method 1): tR=1.81 min; Mass spectrum (ESI+): m/z=182 [M+H]+. Alternatively, the reaction may be conducted in a microwave oven heating with microwave irradiation to 100° C. for 10 min.
c1ccc2c(c1)CCc1ncccc1-2
null
null
null
583,595
ord_dataset-60f3171f0342452f8814e7f294e2be8b
null
2003-01-01T00:02:00
true
Br/[C:2](/[CH3:8])=[CH:3]\[C:4]([O:6][CH3:7])=[O:5].[CH2:9]([NH:16][CH2:17][CH2:18][NH:19][CH2:20][C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1>C1(C)C=CC=CC=1.C(N(CC)CC)C>[CH2:9]([N:16]1[CH2:17][CH2:18][N:19]([CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[CH2:8][CH:2]1[CH2:3][C:4]([O:6][CH3:7])=[O:5])[C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=1
COC(=O)/C=C(/C)Br
c1ccc(CNCCNCc2ccccc2)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCN(CC)CC
Cc1ccccc1
null
null
null
null
null
null
null
null
null
25
24
In toluene (250 ml), N,N′-dibenzylethylenediamine (12 ml) and triethylamine (12 ml) were dissolved, followed by the dropwise addition of methyl 3-bromocrotonate (7.0 ml) under ice cooling. The resulting mixture was stirred at room temperature for 24 hours. After the addition of triethylamine (2.0 ml), the resulting mixture was stirred at room temperature for 71 hours. The insoluble matter was filtered off and the filtrate was distilled under reduced pressure. The residue was added with 10% hydrochloric acid (300 ml) and crystals so precipitated were removed by filtration. Ethyl acetate was added to the filtrate. Potassium carbonate was added to the water layer so separated to make it alkaline. Ethyl acetate was added to the resulting mixture. The organic layer so separated was washed with saturated saline and dried over anhydrous potassium carbonate. The solvent was then distilled off under reduced pressure. The residue was purified by chromatography on a silica gel column (hexane:ethyl acetate=4:1), whereby the title compound (1.07 g, 62%) was obtained.
COC(=O)CC1CN(Cc2ccccc2)CCN1Cc1ccccc1
null
null
null
381,122
ord_dataset-993feac5ecf54388aa6326a220e46db3
null
1997-01-01T00:10:00
true
[CH:1]1[C:17]2[C:16](C(O)=O)=[C:15]3[C:7](=[C:8]4[C:13](=[N:14]3)[CH:12]=[CH:11][CH:10]=[CH:9]4)[NH:6][C:5]=2[CH:4]=[CH:3][CH:2]=1>C1(OC2C=CC=CC=2)C=CC=CC=1>[CH:1]1[C:17]2[CH:16]=[C:15]3[C:7](=[C:8]4[C:13](=[N:14]3)[CH:12]=[CH:11][CH:10]=[CH:9]4)[NH:6][C:5]=2[CH:4]=[CH:3][CH:2]=1
O=C(O)c1c2nc3ccccc3c-2[nH]c2ccccc12
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
c1ccc(Oc2ccccc2)cc1
null
null
null
null
null
null
null
null
null
null
30
null
A mixture of quindoline-11-carboxylic acid prepared in Example 1 (29.2 g, 0.111 mol) and diphenylether (300 mL) was refluxed for 6 hours, cooled to 30° C. and diluted with petroleum ether (250 mL). The precipitate which formed was filtered and washed with petroleum ether thoroughly, yielding 22.1 g (90.9%) of the title compound. A portion of this material was further purified by LPLC (ethyl acetate-hexane 1:3), mp 249°-251° C. [lit 251°-252° C. (Degutis, Y. A.; Ezyarskaite, A. B. Khim. Geterotsik. Soedin. 1986, 1375)]; 1H NMR (DMSO-d6) δ 11.43 (s, 1H, NH), 8.36 (d, J=7.8, 1H), 8.29 (s, 1H), 8.19 (d, J=8.4, 1H), 8.10 (d, J=8.2, 1H), 7.67-7.53 (m, 4H), 7.27 (t, J=7.4, 1H); 13C NMR (DMSO-d6) δ 145.72, 144.03, 143.39, 132.44, 129.68, 128.68, 127.48, 126.71, 126.01, 124.84, 121.34, 120.97, 119.33, 112.99, 111.49; MS (EI, m/z) 218.1 (M+).
c1ccc2[nH]c3c4ccccc4nc-3cc2c1
null
91.2
null
960,129
ord_dataset-ed65749688da45af8a8432967b017729
null
2010-01-01T00:05:00
true
Br[CH2:2][CH2:3][CH2:4][CH2:5][N:6]1[CH2:11][C:10]2[CH:12]=[C:13]([F:16])[CH:14]=[CH:15][C:9]=2[N:8]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=2[F:23])[S:7]1(=[O:25])=[O:24].[CH3:26][NH2:27].Cl>>[F:16][C:13]1[CH:14]=[CH:15][C:9]2[N:8]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=3[F:23])[S:7](=[O:25])(=[O:24])[N:6]([CH2:5][CH2:4][CH2:3][CH2:2][NH:27][CH3:26])[CH2:11][C:10]=2[CH:12]=1
O=S1(=O)N(CCCCBr)Cc2cc(F)ccc2N1c1ccccc1F
CN
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
In an analogous manner to Example 11 step 5, 3-(4-bromobutyl)-6-fluoro-1-(2-fluorophenyl)-3,4-dihydro-1H-2,1,3-benzothiadiazine 2,2-dioxide (0.11 g, 0.25 mmol) was reacted to methylamine and then treated with HCl to provide 4-[6-fluoro-1-(2-fluorophenyl)-2,2-dioxido-1,4-dihydro-3H-2,1,3-benzothiadiazin-3-yl]-N-methylbutan-1-amine (0.085 g, 81%) as a white solid:
CNCCCCN1Cc2cc(F)ccc2N(c2ccccc2F)S1(=O)=O
null
81
null
1,479,023
ord_dataset-c3c1091f873b4f40827973a6f1f9b685
null
2014-01-01T00:09:00
true
[CH:1]1[C:6]2[C:7]3[C:18](=[O:19])[C:17]4[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=4[C:8]=3[O:9][C:10](=O)[C:5]=2[CH:4]=[CH:3][CH:2]=1.[NH2:20][NH2:21]>C(Cl)(Cl)Cl>[NH2:20][N:21]1[C:8]2[C:12]3[CH:13]=[CH:14][CH:15]=[CH:16][C:17]=3[C:18](=[O:19])[C:7]=2[C:6]2[C:5](=[CH:4][CH:3]=[CH:2][CH:1]=2)[C:10]1=[O:9]
O=C1c2ccccc2-c2oc(=O)c3ccccc3c21
NN
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)Cl
null
null
null
null
null
null
null
null
null
null
25
null
Benz[d]indeno[1,2-b]pyran-5,11-dione (4d) (0.150 g, 0.604 mmol) was treated with hydrazine (0.255 g, 7.964 mmol) in CHCl3 (50 mL) and the reaction mixture was heated at reflux for 16 h. The reaction mixture was allowed to cool to room temperature, diluted with CHCl3 (150 mL), and washed with sat NaHCO3 (2×50 mL). The solution was dried over sodium sulfate and concentrated to provide a red-orange solid (0.120 g, 76%): mp 272-274° C. IR (film) 3448, 3305, 1686, 1663, 1610, 1507, 1312, 762 cm−1; 1H NMR (CDCl3) δ 8.54 (d, J=7.8 Hz, 1H), 8.51 (d, J=7.2 Hz, 1H), 8.24 (d, J=7.4 Hz, 1H), 7.85 (m, 1H), 7.60-7.45 (m, 4H), 6.19 (s, 2H); EIMS m/z (rel intensity) 262 (M+, 100). Anal. (C16H10N2O2.0.25H2O) C, H, N.
Nn1c2c(c3ccccc3c1=O)C(=O)c1ccccc1-2
null
75.8
null
557,013
ord_dataset-f483e698250b4da0a84f425c7bfa965a
null
2002-01-01T00:08:00
true
[CH2:1]1[CH2:13][O:12][C:11]2[CH:10]=[CH:9][C:5]([CH2:6][CH2:7][NH2:8])=[CH:4][C:3]=2[O:2]1.Cl[C:15]1[C:16]2[C:28]([CH3:29])=[CH:27][S:26][C:17]=2[N:18]=[C:19]([C:21]2[O:25][N:24]=[CH:23][CH:22]=2)[N:20]=1>>[O:25]1[C:21]([C:19]2[N:20]=[C:15]([NH:8][CH2:7][CH2:6][C:5]3[CH:9]=[CH:10][C:11]4[O:12][CH2:13][CH2:1][O:2][C:3]=4[CH:4]=3)[C:16]3[C:28]([CH3:29])=[CH:27][S:26][C:17]=3[N:18]=2)=[CH:22][CH:23]=[N:24]1
Cc1csc2nc(-c3ccno3)nc(Cl)c12
NCCc1ccc2c(c1)OCCO2
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
With the procedure of Example 1, the reaction of 3,4-ethylenedioxyphenethylamine with 4-chloro-2-(isoxazol-5-yl)-5-methyl-thieno-[2,3-d]-pyrimidine yields 2-(isoxazol-5-yl)-4-(3,4-ethylenedioxyphenethylamino)-5-methyl-thieno-[2,3-d]-pyrimidine.
Cc1csc2nc(-c3ccno3)nc(NCCc3ccc4c(c3)OCCO4)c12
null
null
null
253,669
ord_dataset-cf82113c6dd341d4a014b4667994f01c
null
1992-01-01T00:09:00
true
[O:1]=[C:2]1[N:7]2[N:8]=[CH:9][C:10]3[CH:14]=[CH:13][S:12][C:11]=3[C:6]2=[C:5]([C:15]([OH:17])=[O:16])[CH:4]=[C:3]1[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>[OH-].[K+]>[C:9]([C:10]1[CH:14]=[CH:13][S:12][C:11]=1[C:6]1[NH:7][C:2](=[O:1])[C:3]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:4][C:5]=1[C:15]([OH:17])=[O:16])#[N:8]
O=C(O)c1cc(-c2ccccc2)c(=O)n2ncc3ccsc3c12
null
null
[K+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
48.7 g of 7-oxo-8-phenyl-7H-pyrido[1,2-b]thieno[2,3-d]-pyridazine-10-carboxylic acid were added to a methanolic potassium hydroxide solution (prepared from 72 g of potassium hydroxide and 640 ml of methanol) and the mixture was heated to boiling under reflux for about 24 hours. The reaction mixture was evaporated to half in a vacuum, treated with 80 ml of water and adjusted to pH 1 by the addition of 1N hydrochloric acid. The separated crystals were filtered off under suction, washed with water and dried in a vacuum. There was obtained 48.6 g of 2-(3-cyano-2-thienyl)-1,6-dihydro-6-oxo-5-phenylnicotinic acid as yellow crystals with a m.p. of 255°-257° (methanol/N,N-dimethylformamide).
N#Cc1ccsc1-c1[nH]c(=O)c(-c2ccccc2)cc1C(=O)O
null
99.8
null
616,774
ord_dataset-31fc6d0085ca4d8dbbcd3a5fa9dcedfb
null
2003-01-01T00:11:00
true
[Na+].[C:2]([C:4]1[CH:9]=[CH:8][C:7]([NH:10][S:11](=O)(=[O:13])[O-:12])=[C:6]([O:15][CH3:16])[CH:5]=1)#[N:3].P(Cl)(Cl)(Cl)(Cl)[Cl:18]>O=P(Cl)(Cl)Cl>[C:2]([C:4]1[CH:9]=[CH:8][C:7]([NH:10][S:11]([Cl:18])(=[O:13])=[O:12])=[C:6]([O:15][CH3:16])[CH:5]=1)#[N:3]
ClP(Cl)(Cl)(Cl)Cl
COc1cc(C#N)ccc1NS(=O)(=O)[O-]
null
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O=P(Cl)(Cl)Cl
null
null
null
null
null
null
null
null
null
null
null
null
To a soultion of N-(4-cyano-2-methoxyphenyl)-sulfamic acid sodium salt (1 mmol) at 0° C. in POCl3 (1 mL) is added phosphorous pentachloride (1.2 mmol). Upon reaction completion, the reaction mixture is concentrated and the crude material will be carried onto the next step without further purification.
COc1cc(C#N)ccc1NS(=O)(=O)Cl
null
null
null
747,077
ord_dataset-4b705442211b4a3988e26d5f65098160
null
2006-01-01T00:12:00
true
[C:1]([O:5][C:6](=[O:22])[NH:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[F:20])=[CH:10][C:9]=1[NH2:21])([CH3:4])([CH3:3])[CH3:2].C([O:25][C:26](=O)[CH2:27][C:28]([C:30]1[CH:35]=[C:34]([C:36]#[N:37])[CH:33]=[CH:32][C:31]=1[F:38])=[O:29])C>>[C:1]([O:5][C:6](=[O:22])[NH:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=2[F:20])=[CH:10][C:9]=1[NH:21][C:26](=[O:25])[CH2:27][C:28]([C:30]1[CH:35]=[C:34]([C:36]#[N:37])[CH:33]=[CH:32][C:31]=1[F:38])=[O:29])([CH3:4])([CH3:2])[CH3:3]
CC(C)(C)OC(=O)Nc1ccc(-c2ccccc2F)cc1N
CCOC(=O)CC(=O)c1cc(C#N)ccc1F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Prepared from (3-amino-2′-fluoro-biphenyl-4-yl)-carbamic acid tert.-butyl ester (Example G37) (302 mg, 1.0 mmol) and 3-(5-cyano-2-fluoro-phenyl)-3-oxo-propionic acid ethyl ester (Example H18) (362 mg, 1.5 mmol) according to the general procedure K. Obtained as a yellow-brown solid (352 mg).
CC(C)(C)OC(=O)Nc1ccc(-c2ccccc2F)cc1NC(=O)CC(=O)c1cc(C#N)ccc1F
null
71.6
null
1,454,388
ord_dataset-a86112d52cd54525a5e36d41f18aced2
null
2014-01-01T00:07:00
true
[C:1]([O:5][C:6]([N:8]1[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=2[N:10]=[C:9]1[CH2:17][NH:18][CH:19]1[C:28]2[N:27]=[CH:26][CH:25]=[CH:24][C:23]=2[CH2:22][CH2:21][CH2:20]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[O:29]=[C:30]1[C:38]2[C:33](=[CH:34][CH:35]=[CH:36][CH:37]=2)[C:32](=[O:39])[N:31]1[CH2:40][CH2:41][C:42]1([CH:45]=O)[CH2:44][CH2:43]1.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+]>C(Cl)Cl>[C:1]([O:5][C:6]([N:8]1[C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=2[N:10]=[C:9]1[CH2:17][N:18]([CH2:45][C:42]1([CH2:41][CH2:40][N:31]2[C:30](=[O:29])[C:38]3[C:33](=[CH:34][CH:35]=[CH:36][CH:37]=3)[C:32]2=[O:39])[CH2:44][CH2:43]1)[CH:19]1[C:28]2[N:27]=[CH:26][CH:25]=[CH:24][C:23]=2[CH2:22][CH2:21][CH2:20]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]
CC(C)(C)OC(=O)n1c(CNC2CCCc3cccnc32)nc2ccccc21
O=CC1(CCN2C(=O)c3ccccc3C2=O)CC1
null
CC(=O)O[BH-](OC(C)=O)OC(C)=O
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
null
null
Using General Procedure B: Reaction of (1-tert-butoxycarbonyl-1H-Benzimidazol-2-ylmethyl)-(5,6,7,8-tetrahydro-quinolin-8-yl)-amine (0.269 g, 0.70 mmol) and 1-[2-(1,3-Dioxo-1,3-dihydro-isoindol-2-yl)-ethyl]-cyclopropanecarboxaldehyde (0.25, 1.03 mmol) with NaBH(OAc)3 (0.433 g, 2.04 mmol) in CH2Cl2 (7 mL) for 6 hours followed by purification of the crude material by column chromatography on silica gel (50:1:1 CH2Cl2—CH3OH—NH4OH) followed by radial chromatography on silica gel (1 mm plate, 100:1:1 CH2Cl2—CH3OH—NH4OH) provided 0.125 g (29%) of 2-{[{1-[2-(1,3-Dioxo-1,3-dihydro-isoindol-2-yl)-ethyl]-cyclopropylmethyl}-(5,6,7,8-tetrahydro-quinolin-8-yl)-amino]-methyl}-benzimidazole-1-carboxylic acid tert-butyl ester as a white foam.
CC(C)(C)OC(=O)n1c(CN(CC2(CCN3C(=O)c4ccccc4C3=O)CC2)C2CCCc3cccnc32)nc2ccccc21
null
29.5
null
1,036,519
ord_dataset-3af92aec23dc4810b92eb0d8c60023ee
null
2011-01-01T00:03:00
true
[C:1]([O:5][C:6]([N:8]1[CH2:17][CH2:16][C:15]2[NH:14][N:13]=[C:12]([C:18]3[CH:23]=[CH:22][C:21]([Cl:24])=[CH:20][CH:19]=3)[C:11]=2[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH3:25][O:26][C:27]1[CH:34]=[CH:33][C:30]([CH2:31]Cl)=[C:29]([CH3:35])[CH:28]=1.C(C=P(CCCC)(CCCC)CCCC)#N>C1(C)C=CC=CC=1>[C:1]([O:5][C:6]([N:8]1[CH2:17][CH2:16][C:15]2[N:14]([CH2:31][C:30]3[CH:33]=[CH:34][C:27]([O:26][CH3:25])=[CH:28][C:29]=3[CH3:35])[N:13]=[C:12]([C:18]3[CH:23]=[CH:22][C:21]([Cl:24])=[CH:20][CH:19]=3)[C:11]=2[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:2])[CH3:3]
CC(C)(C)OC(=O)N1CCc2[nH]nc(-c3ccc(Cl)cc3)c2CC1
COc1ccc(CCl)c(C)c1
null
CCCCP(=CC#N)(CCCC)CCCC
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
null
null
null
null
null
null
null
null
null
null
110
null
To a solution of 3-(4-chloro-phenyl)-4,5,7,8-tetrahydro-1H-1,2,6-triaza-azulene-6-carboxylic acid tert-butyl ester (Example 103, Step B; 0.4 mmol) in toluene (3 mL) was added 4-methoxy-2-methyl-benzyl chloride (0.9 mmol) and cyanomethylene-tri-n-butylphosphorane (1 mmol). The mixture was heated at 110° C. for 16 h. After concentration and purification (SiO2, EtOAc/hexanes), 3-(4-chloro-phenyl)-1-(4-methoxy-2-methyl-benzyl)-1,4,5,6,7,8-hexahydro-1,2,6-triaza-azulene-6-carboxylic acid tert-butyl ester was obtained (54 mg). The other regioisomer, 3-(4-chloro-phenyl)-2-(4-methoxy-2-methyl-benzyl)-1,4,5,6,7,8-hexahydro-1,2,6-triaza-azulene-6-carboxylic acid tert-butyl ester, was also obtained (86 mg). 3-(4-Chloro-phenyl)-1-(4-methoxy-2-methyl-benzyl)-1,4,5,6,7,8-hexahydro-1,2,6-triaza-azulene-6-carboxylic acid tert-butyl ester (20 mg) was treated with TFA (1 mL) in CH2Cl2 (10 mL) for 4 h. After concentration of the reaction mixture, the title compound was obtained (0.02 g). MS (ESI): exact mass calculated for C22H24ClN3O, 381.16. found, m/z 382.1 [M+H]+. 1H NMR (500 MHz, CD3OD): 7.39-7.37 (m, 2H), 7.34-7.32 (m, 2H), 6.68-6.66 (br m, 1H), 6.54-6.52 (br m, 1H), 6.37 (d, J=8.3 Hz, 1H), 5.21 (s, 2H), 2.81-2.79 (m, 4H), 2.71-2.69 (m, 4H).
COc1ccc(Cn2nc(-c3ccc(Cl)cc3)c3c2CCN(C(=O)OC(C)(C)C)CC3)c(C)c1
null
null
null
1,623,772
ord_dataset-35c51552812941cda45194a013d34bb9
null
2015-01-01T00:08:00
true
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:20]([O:23][CH2:24][C:25]([NH:27][C:28]1[CH:33]=[CH:32][C:31]([C:34]#[N:35])=[C:30]([O:36][C:37]([F:40])([F:39])[F:38])[CH:29]=1)=O)(=[O:22])[CH3:21].C[Si]([N:45]=[N+:46]=[N-:47])(C)C>C1COCC1>[C:20]([O:23][CH2:24][C:25]1[N:27]([C:28]2[CH:33]=[CH:32][C:31]([C:34]#[N:35])=[C:30]([O:36][C:37]([F:40])([F:39])[F:38])[CH:29]=2)[N:47]=[N:46][N:45]=1)(=[O:22])[CH3:21]
C[Si](C)(C)N=[N+]=[N-]
CC(=O)OCC(=O)Nc1ccc(C#N)c(OC(F)(F)F)c1
null
c1ccc(P(c2ccccc2)c2ccccc2)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
0.5
Triphenylphosphine (17.29 g, 65.7 mmol) and diisopropylazodicorboxylate (13.3 g, 65.7 mmol) were added to a solution of 2-({4-cyano-3-[(trifluoromethyl)oxy]phenyl}amino)-2-oxoethyl acetate (Intermediate 52, 8.0 g, 26.5 mmol) in THF (160 mL) at 0° C. and the mixture was stirred for 30 min. Trimethylsilyl azide (7.60 g, 66.0 mmol) was added dropwise at room temperature and the mixture was heated to reflux for 4 hr. THF was removed under reduced pressure and the residue was diluted with EtOAc and washed with ice-cooled water. The extracted organic layer was washed with brine solution, dried over anhydrous Na2SO4 and concentrated under reduced pressure to afford the crude product. This was purified by column chromatography (100-200 mesh silica gel), eluting with 20% EtOAc/pet ether to give the title compound (7.0 g).
CC(=O)OCc1nnnn1-c1ccc(C#N)c(OC(F)(F)F)c1
null
80.7
null
174,640
ord_dataset-4937da99a6a247eb90fa70f0d2eac3db
null
1988-01-01T00:07:00
true
[CH3:1][C:2]1[NH:3][C:4]([CH3:46])=[C:5]([C:21]([O:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][N:35]2C(=O)C3=CC=CC=C3C2=O)=[O:22])[CH:6]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([N+:18]([O-:20])=[O:19])[CH:13]=2)[C:7]=1[C:8]([O:10][CH3:11])=[O:9].O.NN>>[CH3:1][C:2]1[NH:3][C:4]([CH3:46])=[C:5]([C:21]([O:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH2:32][CH2:33][CH2:34][NH2:35])=[O:22])[CH:6]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([N+:18]([O-:20])=[O:19])[CH:13]=2)[C:7]=1[C:8]([O:10][CH3:11])=[O:9]
COC(=O)C1=C(C)NC(C)=C(C(=O)OCCCCCCCCCCCN2C(=O)c3ccccc3C2=O)C1c1cccc([N+](=O)[O-])c1
null
null
NN
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
null
null
null
null
null
null
null
null
null
null
null
null
Prepared by a method analogous to that of Example 1(b) from 18.95 g (30 mmol) of 1,4-dihydro-2,6-dimethyl-3-methoxycarbonyl-4-(3-nitrophenyl)-5-(11-phthalimido-undecyloxy)carbonyl-pyridine and 4.5 ml (90 mmol) of hydrazine hydrate. 15.0 g of a yellow oil which is used for further reactions without purification.
COC(=O)C1=C(C)NC(C)=C(C(=O)OCCCCCCCCCCCN)C1c1cccc([N+](=O)[O-])c1
null
null
null
1,014,957
ord_dataset-f024e9664ab64906a71a2ff6004cb3d0
null
2010-01-01T00:12:00
true
C(O[C:6]([N:8]1[CH2:13][CH2:12][O:11][C@H:10]([CH2:14][OH:15])[CH2:9]1)=O)(C)(C)C.[H-].[H-].[H-].[H-].[Li+].[Al+3]>C1COCC1>[CH3:6][N:8]1[CH2:13][CH2:12][O:11][C@H:10]([CH2:14][OH:15])[CH2:9]1
CC(C)(C)OC(=O)N1CCO[C@H](CO)C1
null
null
[Al+3]
[H-]
[Li+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
0.25
(S)-2-Hydroxymethyl-morpholine-4-carboxylic acid tert-butyl ester (Intermediate 8; 1.20 g, 5.52 mmol) in THF (5 mL) was added to a suspension of LiAlH4 (1.30 g, 34.3 mmol) in anhydrous THF (15 mL) at −10° C. and stirred under nitrogen for 15 min. The cooling bath was removed and the reaction mixture was gently heated to reflux for 4 h. The reaction mixture was quenched by careful addition of a mixture of water (4 mL) in THF (25 mL) with ice bath cooling. THF (50 mL) was added to the reaction mixture, stirred for 15 min, filtered and the solid washed with THF (50 mL). The combined filtrates were evaporated in vacuo. The residue was dissolved in DCM (50 mL), dried (MgSO4) and the solvent removed in vacuo to give (S)-(4-methylmorpholin-2-yl)-methanol (490 mg, 67%) as a colourless oil.
CN1CCO[C@H](CO)C1
null
67.7
null
931,609
ord_dataset-d8a5dc784dde4465894ec7c69d2e3ba6
null
2010-01-01T00:01:00
true
[CH:1]1([N:6]2[C:11]3[N:12]=[C:13]([S:16][CH3:17])[N:14]=[CH:15][C:10]=3[CH:9]=[C:8]([C:18]3[CH:23]=[C:22]([C:24]4[O:25][C:26]([CH2:29][CH:30]([CH3:32])[CH3:31])=[N:27][N:28]=4)[CH:21]=[CH:20][C:19]=3[CH3:33])[C:7]2=[O:34])[CH2:5][CH2:4][CH2:3][CH2:2]1.ClC1C=C(C=CC=1)C(OO)=[O:40]>ClCCl.C(OCC)(=O)C>[CH:1]1([N:6]2[C:11]3[N:12]=[C:13]([S:16]([CH3:17])=[O:40])[N:14]=[CH:15][C:10]=3[CH:9]=[C:8]([C:18]3[CH:23]=[C:22]([C:24]4[O:25][C:26]([CH2:29][CH:30]([CH3:32])[CH3:31])=[N:27][N:28]=4)[CH:21]=[CH:20][C:19]=3[CH3:33])[C:7]2=[O:34])[CH2:2][CH2:3][CH2:4][CH2:5]1
CSc1ncc2cc(-c3cc(-c4nnc(CC(C)C)o4)ccc3C)c(=O)n(C3CCCC3)c2n1
O=C(OO)c1cccc(Cl)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOC(C)=O
ClCCl
null
null
null
null
null
null
null
null
null
0
1
To a solution of 8-cyclopentyl-6-{5-(5-isobutyl-[1,3,4]oxadiazol-2-yl)-2-methyl-phenyl}-2-methylsulfanyl-8H-pyrido[2,3-d]pyrimidin-7-one (40.0 mg, 0.08 mmol) in dichloromethane (3 mL) at 0° C. was added 3-chloroperoxybenzoic acid (0.04 g, 0.19 mmol). The mixture was stirred at 0° C. for 1 hour, then was diluted with ethyl acetate. The organic layer was washed with saturated sodium bicarbonate solution and brine, dried (magnesium sulfate), filtered and concentrated under reduced pressure to give 8-cyclopentyl-6-{5-(5-isobutyl-[1,3,4]-oxadiazol-2-yl)-2-methyl-phenyl}-2-methanesulfinyl-8H-pyrido[2,3-d]pyrimidin-7-one (0.06 g). The crude product was used in the next step without further purification.
Cc1ccc(-c2nnc(CC(C)C)o2)cc1-c1cc2cnc(S(C)=O)nc2n(C2CCCC2)c1=O
null
152.6
null
955,788
ord_dataset-ed65749688da45af8a8432967b017729
null
2010-01-01T00:05:00
true
ClCC([NH:5][C:6]1[C:11]([N+:12]([O-:14])=[O:13])=[CH:10][CH:9]=[C:8]([F:15])[C:7]=1[CH3:16])=O.[OH-].[Na+].O1CCCC1>O>[F:15][C:8]1[C:7]([CH3:16])=[C:6]([C:11]([N+:12]([O-:14])=[O:13])=[CH:10][CH:9]=1)[NH2:5]
Cc1c(F)ccc([N+](=O)[O-])c1NC(=O)CCl
null
null
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
2-Chloro-N-(3-fluoro-2-methyl-6-nitrophenyl)acetamide (prepared from 47.2 g of 2-chloro-N-(3-fluoro-2-methylphenyl)acetamide, ca. 234 mmol) was suspended in water (220 ml) then treated with aqueous sodium hydroxide solution (12.5M, 110 ml, 1.37 mol). Tetrahydrofuran (110 ml) was added, then the mixture was heated to reflux for 5 hours, then evaporated (removing most of the tetrahydrofuran). The yellow solid was filtered off and washed with water until washing were non-alkaline. Drying in vacuo afforded a yellow solid (32.3 g, 81% over 2 steps) containing ˜13% isomer.
Cc1c(F)ccc([N+](=O)[O-])c1N
null
null
null
1,078,050
ord_dataset-afd812677c134591a99f46ce28de2524
null
2011-01-01T00:08:00
true
Cl[C:2]1[N:7]=[C:6]([C:8]2[S:12][C:11]([CH:13]3[CH2:18][CH2:17][O:16][CH2:15][CH2:14]3)=[N:10][C:9]=2[C:19]2[C:20]([F:34])=[C:21]([NH:25][S:26]([C:29]3[CH:33]=[CH:32][O:31][CH:30]=3)(=[O:28])=[O:27])[CH:22]=[CH:23][CH:24]=2)[CH:5]=[CH:4][N:3]=1.[CH3:35][Zn]C>>[F:34][C:20]1[C:19]([C:9]2[N:10]=[C:11]([CH:13]3[CH2:18][CH2:17][O:16][CH2:15][CH2:14]3)[S:12][C:8]=2[C:6]2[CH:5]=[CH:4][N:3]=[C:2]([CH3:35])[N:7]=2)=[CH:24][CH:23]=[CH:22][C:21]=1[NH:25][S:26]([C:29]1[CH:33]=[CH:32][O:31][CH:30]=1)(=[O:28])=[O:27]
C[Zn]C
O=S(=O)(Nc1cccc(-c2nc(C3CCOCC3)sc2-c2ccnc(Cl)n2)c1F)c1ccoc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Following a procedure analogous to the procedure described in Example 25 using N-{3-[5-(2-chloro-4-pyrimidinyl)-2-(tetrahydro-2H-pyran-4-yl)-1,3-thiazol-4-yl]-2-fluorophenyl}-3-furansulfonamide (200 mg, 0.384 mmol)mmol) and dimethylzinc (384 μl, 0.768 mmol) at 80° C. for 3 hours, the title compound was obtained as a solid (60 mg, 31% yield). MS (ESI): 500.8 [M+H]+
Cc1nccc(-c2sc(C3CCOCC3)nc2-c2cccc(NS(=O)(=O)c3ccoc3)c2F)n1
null
null
null
1,417,781
ord_dataset-f8e6e6a2d2bf4135b9e346456c81700f
null
2014-01-01T00:04:00
true
Cl[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][N:3]=1.Cl.[F:12][C:13]1([F:19])[CH2:18][CH2:17][NH:16][CH2:15][CH2:14]1.C(N(CC)C(C)C)(C)C>C(O)C>[F:12][C:13]1([F:19])[CH2:18][CH2:17][N:16]([C:2]2[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][N:3]=2)[CH2:15][CH2:14]1
FC1(F)CCNCC1
O=[N+]([O-])c1ccc(Cl)nc1
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
CCN(C(C)C)C(C)C
null
null
null
null
null
null
null
null
null
70
null
To a slurry of 2-chloro-5-nitropyridine (5 g, 31.5 mmol) and 4,4-difluoropiperidine hydrochloride (4.97 g) in ethanol (40 mL) at ambient temperature was added N,N-diisopropylethylamine (12.00 mL, 69.4 mmol) and the mixture heated to 70° C. for 18 hours. The reaction was concentrated, partitioned between CH2Cl2 and 1M NaOH. The organic phase concentrated and purified by chromatography (elution with 2% MeOH—CH2Cl2 then 3% MeOH—CH2Cl2) to provide the title compound as a yellow oil. MS (DCI) m/z 261 (M+NH4)+.
O=[N+]([O-])c1ccc(N2CCC(F)(F)CC2)nc1
null
null
null
653,058
ord_dataset-fe016e2f90e741a590ad77fd5933161f
null
2004-01-01T00:11:00
true
C([O:8][C:9]1[CH:25]=[CH:24][C:12]([CH2:13][NH:14][C:15]2[C:20]([Cl:21])=[C:19](C)[N:18]=[C:17]([CH3:23])[N:16]=2)=[CH:11][C:10]=1[O:26][CH:27]([F:29])[F:28])C1C=CC=CC=1.Cl.[CH2:31](O)C>>[Cl:21][C:20]1([CH3:31])[CH:19]=[N:18][C:17]([CH3:23])=[N:16][CH:15]1[NH:14][CH2:13][C:12]1[CH:24]=[CH:25][C:9]([OH:8])=[C:10]([O:26][CH:27]([F:28])[F:29])[CH:11]=1
CCO
Cc1nc(C)c(Cl)c(NCc2ccc(OCc3ccccc3)c(OC(F)F)c2)n1
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
In analogy to the method described in example B1, 6.9 g (16.4 mmol) of [4-benzyloxy-3-(1.1-difluoromethoxy)benzyl](5-chloro-2,6-dimethylpyrimidin-4-yl)amine (from example A6) are reacted with 70 ml of 12.5N hydrochloric acid in 70 ml of ethanol. Extraction with ethyl acetate at a pH of 8 gives, after concentration, a solid residue. Extraction by stirring with petroleum ether and drying give 2.2 g (41%) of the title compound as a beige crystallizate. m.p.: 167-168.5° C.
CC1=NC(NCc2ccc(O)c(OC(F)F)c2)C(C)(Cl)C=N1
null
41
null
1,051,059
ord_dataset-dd320ded4b3f4764af39de99491533f7
null
2011-01-01T00:04:00
true
[C:1]([C:3]1[CH:4]=[C:5]([CH:9]=[CH:10][CH:11]=1)[C:6](Cl)=[O:7])#[CH:2].[C:12]1([OH:18])[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.N1C=CC=CC=1>ClCCl>[C:1]([C:3]1[CH:4]=[C:5]([CH:9]=[CH:10][CH:11]=1)[C:6]([O:18][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[O:7])#[CH:2]
Oc1ccccc1
C#Cc1cccc(C(=O)Cl)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
c1ccncc1
null
null
null
null
null
null
null
null
null
null
null
Air in a 20 ml Schlenk tube was replaced by Ar gas and 1.02 g (7 mmol) of m-ethynylbenzoic acid and 5 g (42 mmol) of thionyl chloride were added to the tube and the mixture was stirred at 50° C. for 2 hours and then excess thionyl chloride was removed by distillation under reduced pressure to obtain m-ethynylbenzoyl chloride. To the m-ethynylbenzoyl chloride obtained was added a solution having 692 mg (7.35 mmol) of phenol and 3.4 ml (42 mmol) of pyridine dissolved in 7 ml of dichloromethane under ice-cooling and then the resultant mixture was stirred at room temperature for one hour. After completion of the stirring, dichloromethane was removed by distillation under reduced pressure and 35 ml of water was added to the resultant residue. The mixture was extracted with 35 ml of ethyl acetate, the extract was dried over magnesium sulfate and the solvent was removed by distillation under reduced pressure using an evaporator. The resultant crude reaction product was purified by column chromatography (Hexane/AcOEt=10/1) using silica gel to obtain 0.55 q of phenyl 3-ethynylbenzoate which is a desired product as yellow solid. (Yield: 35%)
C#Cc1cccc(C(=O)Oc2ccccc2)c1
null
null
null
153,173
ord_dataset-128a4f3f44e844218b1c319ab4de3893
null
1987-01-01T00:02:00
true
Cl[Si:2]([CH3:10])([CH3:9])[CH2:3][CH2:4][Si:5](Cl)([CH3:7])[CH3:6].[NH2:11][CH:12]1[C:33](=[O:34])[N:14]2[C:15]([C:20]([O:22][CH2:23][C:24]3[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][CH:25]=3)=[O:21])=[C:16]([Cl:19])[CH2:17][S:18][C@H:13]12.C(N(CC)CC)C>C(Cl)Cl>[Cl:19][C:16]1[CH2:17][S:18][C@@H:13]2[CH:12]([N:11]3[Si:5]([CH3:7])([CH3:6])[CH2:4][CH2:3][Si:2]3([CH3:10])[CH3:9])[C:33](=[O:34])[N:14]2[C:15]=1[C:20]([O:22][CH2:23][C:24]1[CH:29]=[CH:28][C:27]([N+:30]([O-:32])=[O:31])=[CH:26][CH:25]=1)=[O:21]
NC1C(=O)N2C(C(=O)OCc3ccc([N+](=O)[O-])cc3)=C(Cl)CS[C@H]12
C[Si](C)(Cl)CC[Si](C)(C)Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
CCN(CC)CC
null
null
null
null
null
null
null
null
null
25
null
A solution of 1,2-bis(chlorodimethylsilyl)ethane (3.2 g) in methylene chloride (20 ml) was added to a stirred mixture of p-nitrobenzyl 7-amino-3-chloro-3-cephem-4-carboxylate (5.0 g) and triethylamine (4.9 ml) in methylene chloride (25 ml) under a nitrogen atmosphere. The mixture was stirred at reflux for 16 hours, then allowed to cool to room temperature, and washed with 8% aqueous sodium hydrogen phosphate solution. The organic layer was separated, dried with magnesium sulphate, and evaporated under reduced pressure to give the title compound as a gum, nmr (CDCl3) δ0.17 (s, 12H), 0.78 (s, 4H), 3.38+3.82 (ABq, J=18 Hz, 2H), 4.76 (d, J=4 Hz, 1H), 4.93 (d, J=4 Hz, 1H), 5.28 (s, 2H), 7.3-8.1 (m, 4H).
C[Si]1(C)CC[Si](C)(C)N1C1C(=O)N2C(C(=O)OCc3ccc([N+](=O)[O-])cc3)=C(Cl)CS[C@H]12
null
null
null
821,743
ord_dataset-ec58fad8331a42c5a67ad75aac6713b4
null
2008-01-01T00:05:00
true
[NH2:1][CH:2]1[C:8](=[O:9])[N:7]([CH3:10])[C:6]2[CH:11]=[CH:12][CH:13]=[CH:14][C:5]=2[C:4]2[CH:15]=[CH:16][CH:17]=[CH:18][C:3]1=2.[CH3:19][CH:20]([C:24]([NH:26][CH2:27][C:28]1[CH:33]=[CH:32][C:31]([CH3:34])=[CH:30][CH:29]=1)=[O:25])[C:21](O)=[O:22]>>[CH3:19][CH:20]([C:21]([NH:1][CH:2]1[C:8](=[O:9])[N:7]([CH3:10])[C:6]2[CH:11]=[CH:12][CH:13]=[CH:14][C:5]=2[C:4]2[CH:15]=[CH:16][CH:17]=[CH:18][C:3]1=2)=[O:22])[C:24]([NH:26][CH2:27][C:28]1[CH:29]=[CH:30][C:31]([CH3:34])=[CH:32][CH:33]=1)=[O:25]
Cc1ccc(CNC(=O)C(C)C(=O)O)cc1
CN1C(=O)C(N)c2ccccc2-c2ccccc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound, MS: m/e=441.2 (M+H+), was prepared in analogy to example 16 from 7-amino-5-methyl-5H,7H-dibenzo[b,d]azepin-6-one and 2-methyl-N-(4-methyl-benzyl)-malonamic acid.
Cc1ccc(CNC(=O)C(C)C(=O)NC2C(=O)N(C)c3ccccc3-c3ccccc32)cc1
null
null
null
1,747,553
ord_dataset-60a3e71da3174666a50a61dcfa611a9f
null
2016-01-01T00:07:00
true
[OH:1][NH:2][C:3]1[CH:13]=[CH:12][CH:11]=[CH:10][C:4]=1[C:5]([O:7][CH2:8][CH3:9])=[O:6].Br[CH2:15][C:16]1[N:17]=[C:18]([C:21]([F:24])([F:23])[F:22])[S:19][CH:20]=1>>[F:22][C:21]([F:24])([F:23])[C:18]1[S:19][CH:20]=[C:16]([CH2:15][O:1][NH:2][C:3]2[CH:13]=[CH:12][CH:11]=[CH:10][C:4]=2[C:5]([O:7][CH2:8][CH3:9])=[O:6])[N:17]=1
FC(F)(F)c1nc(CBr)cs1
CCOC(=O)c1ccccc1NO
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The titled compound was prepared using similar procedure as that of Example-1 (step-2) using ethyl 2-(hydroxyamino)benzoate and product of step 3 described above in 52% yield.
CCOC(=O)c1ccccc1NOCc1csc(C(F)(F)F)n1
null
52
null
1,548,302
ord_dataset-cac8df8aff894288876df4e093c9877f
null
2015-01-01T00:02:00
true
[NH:1]1[C:5]2[CH:6]=[CH:7][CH:8]=[CH:9][C:4]=2[N:3]=[C:2]1[C:10]([OH:12])=O.CN(C(ON1N=NC2C=CC=NC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F.Cl.[NH:38]1[CH2:41][CH:40]([C:42]2[C:47]([C:48]3[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=3)=[CH:46][CH:45]=[CH:44][N:43]=2)[CH2:39]1>CN(C=O)C.O>[NH:3]1[C:4]2[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=2[N:1]=[C:2]1[C:10]([N:38]1[CH2:39][CH:40]([C:42]2[C:47]([C:48]3[CH:53]=[CH:52][CH:51]=[CH:50][CH:49]=3)=[CH:46][CH:45]=[CH:44][N:43]=2)[CH2:41]1)=[O:12]
c1ccc(-c2cccnc2C2CNC2)cc1
O=C(O)c1nc2ccccc2[nH]1
null
CN(C)C(On1nnc2cccnc21)=[N+](C)C
Cl
F[P-](F)(F)(F)(F)F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
0.08
To a mixture of 1H-benzoimidazole-2-carboxylic acid (124 mg, 0.76 mmol) in DMF (5 mL) was added TEA (152 mg, 1.5 mmol) and HATU (347 mg, 0.92 mmol). The reaction mixture was stirred for 5 min and 2-azetidin-3-yl-3-phenyl-pyridine hydrochloride (100 mg, 0.76 mmol) was added. The reaction mixture was stirred at RT overnight. The mixture was diluted with water (10 mL), and extracted with EtOAc (2×20 mL). The combined organic extracts were washed with water (5 mL) and brine (5 mL), dried over Na2SO4, and filtered. The filtrate was evaporated in vacuo and the residue was purified by column chromatography to give (1H-benzoimidazol-2-yl)-[3-(3-phenyl-pyridin-2-yl)-azetidin-1-yl]-methanone (100 mg, 0.28 mmol, 59% yield) as a light yellow solid.
O=C(c1nc2ccccc2[nH]1)N1CC(c2ncccc2-c2ccccc2)C1
null
36.8
null
1,429,570
ord_dataset-5e6956e6e8c24a168866a253f4a66c6c
null
2014-01-01T00:05:00
true
[C:1]([C:3]1[CH:27]=[CH:26][C:6]([O:7][C:8]2[CH:9]=[C:10]([CH:14]=[C:15]([O:17][C:18]3[CH:23]=[CH:22][C:21]([C:24]#[N:25])=[CH:20][CH:19]=3)[CH:16]=2)[C:11](O)=[O:12])=[CH:5][CH:4]=1)#[N:2].[C:28]([O:32][C:33]([N:35]1[CH2:40][CH2:39][NH:38][CH2:37][CH2:36]1)=[O:34])(C)(C)[CH3:29]>>[CH2:28]([O:32][C:33]([N:35]1[CH2:36][CH2:37][N:38]([C:11](=[O:12])[C:10]2[CH:14]=[C:15]([O:17][C:18]3[CH:19]=[CH:20][C:21]([C:24]#[N:25])=[CH:22][CH:23]=3)[CH:16]=[C:8]([O:7][C:6]3[CH:5]=[CH:4][C:3]([C:1]#[N:2])=[CH:27][CH:26]=3)[CH:9]=2)[CH2:39][CH2:40]1)=[O:34])[CH3:29]
N#Cc1ccc(Oc2cc(Oc3ccc(C#N)cc3)cc(C(=O)O)c2)cc1
CC(C)(C)OC(=O)N1CCNCC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Following the procedure of Example 5(c) 3,5-bis-(4-cyano-phenoxy)-benzoic acid 0.45 g (1.26 mmol) and piperazine-1-carboxylic acid tert-butyl ester (0.234 g, 1.26 mmol) were used to afford 0.5 g of the required product. 1H NMR (DMSO-d6): δ 1.18 (3H, t), 3.52 (8H, m), 4.15 (2H, q), 7.00 (2H, s), 7.07 (1H, s), 7.28 (2H, d), 7.88 (2H, d).
CCOC(=O)N1CCN(C(=O)c2cc(Oc3ccc(C#N)cc3)cc(Oc3ccc(C#N)cc3)c2)CC1
null
79.9
null
1,152,194
ord_dataset-b195433d5c354ddfb6cde0d53c41910f
null
2012-01-01T00:04:00
true
Cl[C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=2)[C:5]([Cl:12])=[N:4][N:3]=1.[CH3:13][C@H:14]1[CH2:19][NH:18][C@H:17]([CH3:20])[CH2:16][NH:15]1>ClCCl>[Cl:12][C:5]1[C:6]2[C:11](=[CH:10][CH:9]=[CH:8][CH:7]=2)[C:2]([N:15]2[CH2:16][C@@H:17]([CH3:20])[NH:18][CH2:19][C@@H:14]2[CH3:13])=[N:3][N:4]=1
C[C@@H]1CN[C@@H](C)CN1
Clc1nnc(Cl)c2ccccc12
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
130
null
1,4-dichlorophthalazine (1.0 g, 5 mmole) and trans-2,5-dimethyl piperazine were combined in a reaction vial and heated to 130° C. for 3 h with stirring. After cooling to room temperature, the solid residue was dissolved in 150 mL of dichloromethane and washed with 1×20 mL of 1:1 saturated NaHCO3 solution:H2O and 1×20 mL of saturated NaCl solution. The organic phase was dried over MgSO4, filtered, and concentrated. Purification by column chromatography (100:5:1 dichloromethane:methanol:triethylamine) afforded 1-chloro-4-(trans-2,5-dimethylpiperazin-1-yl)phthalazine. MS (M+H)+=277.1.
C[C@@H]1CN(c2nnc(Cl)c3ccccc23)[C@@H](C)CN1
null
null
null
626,895
ord_dataset-e44331dc51de453ca14b7032593c1958
null
2004-01-01T00:02:00
true
[NH2:1][C:2]1[C:11]2[C:6](=[CH:7][CH:8]=[CH:9][C:10]=2[O:12][C:13]2[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][CH:14]=2)[N:5]=[CH:4][N:3]=1.[CH3:21][O:22][C:23]1[CH:24]=[C:25]([N:29]=[C:30]=[O:31])[CH:26]=[CH:27][CH:28]=1>ClCCl>[CH3:20][O:19][C:16]1[CH:17]=[CH:18][C:13]([O:12][C:10]2[CH:9]=[CH:8][CH:7]=[C:6]3[C:11]=2[C:2]([NH:1][C:30]([NH:29][C:25]2[CH:26]=[CH:27][CH:28]=[C:23]([O:22][CH3:21])[CH:24]=2)=[O:31])=[N:3][CH:4]=[N:5]3)=[CH:14][CH:15]=1
COc1ccc(Oc2cccc3ncnc(N)c23)cc1
COc1cccc(N=C=O)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
null
null
4-Amino-5-(4-methoxyphenoxy)quinazoline (0.35 g, 1.3 mmol) and 3-methoxyphenyl isocyanate (0.23 g, 1.6 mmol) were reacted in 20 ml of dichloromethane according to procedure E to give 1-[5-(4-methoxyphenoxy)quinazolin-4-yl]-3-(3-methoxyphenyl)urea (0.4 g, 74.1%, m.p. 209-210° C.).
COc1ccc(Oc2cccc3ncnc(NC(=O)Nc4cccc(OC)c4)c23)cc1
null
73.9
null
351,542
ord_dataset-127eb5fdd5b4402e92b51d0b55a5dcb5
null
1997-01-01T00:01:00
true
[CH3:1][O:2][CH2:3][C:4]([Cl:6])=[O:5].[Cl-].[C:8]([O:11][CH:12]([CH2:30][O:31][C:32](=[O:34])[CH3:33])[CH2:13][NH:14][C:15](=[O:29])[C:16]1[C:24]([I:25])=[C:23]([NH2:26])[C:22]([I:27])=[C:18]([C:19]([OH:21])=[O:20])[C:17]=1[I:28])(=[O:10])[CH3:9]>O1CCOCC1>[Cl-:6].[C:8]([O:11][CH:12]([CH2:30][O:31][C:32](=[O:34])[CH3:33])[CH2:13][NH:14][C:15](=[O:29])[C:16]1[C:24]([I:25])=[C:23]([NH:26][C:4](=[O:5])[CH2:3][O:2][CH3:1])[C:22]([I:27])=[C:18]([C:19]([OH:21])=[O:20])[C:17]=1[I:28])(=[O:10])[CH3:9]
COCC(=O)Cl
CC(=O)OCC(CNC(=O)c1c(I)c(N)c(I)c(C(=O)O)c1I)OC(C)=O
null
[Cl-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1COCCO1
null
null
null
null
null
null
null
null
null
null
25
null
24.7 g (150 mmol) of methoxyacetyl chloride is added to a suspension of 73.4 g (100 mmol) of 5-amino-2,4,6-triiodoisophthalic acid-N-(2,3-diacetoxypropyl)-amide-chloride (EP 0308364) in 500 ml of anhydrous dioxane, stirred with exclusion of moisture, at room temperature. The batch is refluxed for several hours, until, according to thin-layer chromatography, feedstock is no longer detectable, then it is concentrated by evaporation, the residue is taken up in dichloromethane and shaken out with saturated aqueous sodium bicarbonate solution. After drying on anhydrous magnesium sulfate, the organic phase is concentrated by evaporation, and the residue is recrystallized from ethyl acetate/tert-butyl methyl ether.
COCC(=O)Nc1c(I)c(C(=O)O)c(I)c(C(=O)NCC(COC(C)=O)OC(C)=O)c1I
null
null
null
818,778
ord_dataset-50f99930fc41474db226bc80774b38df
null
2008-01-01T00:04:00
true
[CH2:1]([N:8]1[C:13]2[S:14][CH:15]=[C:16]([CH3:17])[C:12]=2[C:11](=[O:18])O[C:9]1=[O:19])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:20]([O:22][C:23]([C:25]1C(=O)N(CC2C=CC=CC=2)C2SC=CC=2C=1O)=[O:24])[CH3:21]>>[CH2:20]([O:22][C:23]([C:25]1[C:9](=[O:19])[N:8]([CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[C:13]2[S:14][CH:15]=[C:16]([CH3:17])[C:12]=2[C:11]=1[OH:18])=[O:24])[CH3:21]
CCOC(=O)c1c(O)c2ccsc2n(Cc2ccccc2)c1=O
Cc1csc2c1c(=O)oc(=O)n2Cc1ccccc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
This compound was prepared from 1-benzyl-5-methyl-1H-thieno[2,3-d][1,3]oxazine-2,4-dione (59) by applying the same method described for the preparation of 7-benzyl-4-hydroxy-6-oxo-6,7-dihydro-thieno[2,3-b]pyridine-5-carboxylic acid ethyl ester (60). Yield 80%; MP 166° C. 1H-NMR (DMSO-d6): δ 1.32 (t, J=6.8 Hz, 3H), 2.40 (d, J=1.2 Hz, 3H), 4.36 (q, J=6.8 Hz, 2H), 5.22 (s, 2H), 6.84 (d, J=1.2 Hz, 1H), 7.25 (m, 3H), 7.32 (m, 2H), 14.04 (b, 1H) ppm; EIMS m/z 344 (M+1).
CCOC(=O)c1c(O)c2c(C)csc2n(Cc2ccccc2)c1=O
null
80
null
180,726
ord_dataset-ed5a3d1f8dc744759e7fa1c320a44e59
null
1988-01-01T00:11:00
true
[CH3:1][C:2]1([C:7]2[CH:8]=[CH:9][C:10]3[CH:14]=[C:13]([S:15](=[O:18])(=[O:17])[NH2:16])[S:12][C:11]=3[CH:19]=2)OCC[O:3]1.C1(C)C=CC(S(O)(=O)=O)=CC=1>CC(C)=O>[C:2]([C:7]1[CH:8]=[CH:9][C:10]2[CH:14]=[C:13]([S:15](=[O:18])(=[O:17])[NH2:16])[S:12][C:11]=2[CH:19]=1)(=[O:3])[CH3:1]
CC1(c2ccc3cc(S(N)(=O)=O)sc3c2)OCCO1
null
null
Cc1ccc(S(=O)(=O)O)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(C)=O
null
null
null
null
null
null
null
null
null
null
null
8
The ketal product from Example 37 (4.4 g, 14.7 mmole) and p-toluenesulfonic acid (400 mg) were dissolved in acetone (90 ml). The mixture was stirred overnight. The solvent was removed in vacuo and the residue partitioned between ethyl acetate (200 ml) and 10% saturated NaHCO3 solution (b 100 ml). The organic layer was washed with H2O (2×100 ml) and dried over Na2SO4. The solvent was removed in vacuo and the residue was triturated with hot CHCl3 (100 ml). Upon cooling, 3.4 g (90.6%) of product was obtained, m.p. 154°-155° C.
CC(=O)c1ccc2cc(S(N)(=O)=O)sc2c1
null
90.6
null
374,601
ord_dataset-ee5599340390470d8e5b5ac1feddf9d6
null
1997-01-01T00:08:00
true
[C:1]([NH:4][C:5]1[CH:14]=[C:13]([F:15])[C:12]([F:16])=[C:11]2[C:6]=1[CH2:7][CH2:8][CH2:9][C:10]2=O)(=[O:3])[CH3:2].C(O)C.[BH4-].[Na+].C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C(Cl)(Cl)Cl>[C:1]([NH:4][C:5]1[CH:14]=[C:13]([F:15])[C:12]([F:16])=[C:11]2[C:6]=1[CH2:7][CH2:8][CH2:9][CH2:10]2)(=[O:3])[CH3:2]
CC(=O)Nc1cc(F)c(F)c2c1CCCC2=O
null
null
O=C(O)CC(O)(CC(=O)O)C(=O)O
[BH4-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)Cl
CCO
null
null
null
null
null
null
null
null
null
25
null
The compound obtained in (5) above (1 gm) was dissolved into 20 ml of ethanol. To the solution was added 166 mg of sodium borohydride while stirring at room temperature. After stirring for 20 minutes, chloroform and 10% citric acid were added to the reaction mixture. The chloroform layer was extracted and concentrated. To the concentrate were added 20 ml of toluene and a small amount of p-TsOH, followed by heating under reflux for 1 hour. Upon addition of 100 ml of ethyl acetate, the reaction product was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was evaporated and the residue was dissolved into a mixed solvent of 20 ml of ethanol, 20 ml of dioxane, and 0.2 ml of acetic acid. The mixture was catalytically hydrogenated with the addition of 200 mg of platinum oxide. The catalyst was removed, the filtrate was concentrated, and ether was added to the concentrate. 0.8 gm of the title compound was obtained by collecting the precipitate by filtration.
CC(=O)Nc1cc(F)c(F)c2c1CCCC2
null
null
null
981,511
ord_dataset-35b56288528641309a040cc2b6710b61
null
2010-01-01T00:08:00
true
[CH3:1][C:2]([CH3:16])([CH3:15])[C:3](=[O:14])[CH2:4][N:5]1[CH2:12][CH:11]2[O:13][CH:7]([CH2:8][NH:9][CH2:10]2)[CH2:6]1.CS(O[CH2:22][CH2:23][C:24]1[CH:29]=[CH:28][C:27]([C:30]#[N:31])=[CH:26][CH:25]=1)(=O)=O>CC#N>[CH3:1][C:2]([CH3:16])([CH3:15])[C:3](=[O:14])[CH2:4][N:5]1[CH2:12][CH:11]2[O:13][CH:7]([CH2:8][N:9]([CH2:22][CH2:23][C:24]3[CH:29]=[CH:28][C:27]([C:30]#[N:31])=[CH:26][CH:25]=3)[CH2:10]2)[CH2:6]1
CS(=O)(=O)OCCc1ccc(C#N)cc1
CC(C)(C)C(=O)CN1CC2CNCC(C1)O2
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC#N
null
null
null
null
null
null
null
null
null
null
50
24
A mixture of 3,3-dimethyl-1-(9-oxa-3,7-diazabicyclo[3.3.1]non-3-yl)-2-butanone (from step (ii) above; 56 mg, 0.25 mmol), TEA (0.35 mL, 2.5 mmol) and MeCN (2 mL) was treated with 4-cyanophenethyl methanesulfonate (see step (iii) above; 84 mg, 0.37 mmol). The resulting mixture was stirred at 50° C. for 24 h. The solvents were removed by evaporation, the crude product was dissolved in DCM and then the solution was added to an ion-exchange solid-phase extraction plug (2 g, CBA (carboxylic acid on silica support)). After 1 h, the plug was washed with DCM (15 mL), after which the product was finally eluted with DCM:MeOH:TEA (90:5:5), to give 84 mg (95%) of the title compound.
CC(C)(C)C(=O)CN1CC2CN(CCc3ccc(C#N)cc3)CC(C1)O2
null
95
null
411,124
ord_dataset-fbdd058349aa456f812e3546c84baab5
null
1998-01-01T00:09:00
true
Cl.[NH2:2][CH:3]1[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([O:12][CH3:13])[CH:10]=2)[N:5]([C:14]2[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=2)[C:4]1=[O:21].C(=O)([O-])[O-].[K+].[K+].[C:28](#[N:31])[CH:29]=[CH2:30]>CS(C)=O>[NH2:2][C:3]1([CH2:30][CH2:29][C:28]#[N:31])[C:11]2[C:6](=[CH:7][CH:8]=[C:9]([O:12][CH3:13])[CH:10]=2)[N:5]([C:14]2[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=2)[C:4]1=[O:21]
C=CC#N
COc1ccc2c(c1)C(N)C(=O)N2c1ccc(F)cc1
null
Cl
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CS(C)=O
null
null
null
null
null
null
null
null
null
null
25
2
A mixture of 60 g of 3-amino-1-(4-fluorophenyl)-2,3-dihydro-5-methoxy-1H-indol-2-one hydrochloride, 43 g of potassium carbonate, 20 ml of acrylonitrile and 200 ml of dimethyl sulfoxide was stirred at room temperature under argon atmosphere for 2 hours. 2 ml of acrylonitrile was added to the mixture, and stirring was continued overnight. The reaction mixture was poured into ice water and extracted with ethyl acetate. The extract was washed with a saturated sodium chloride solution, dried over anhydrous magnesium sulfate and filtered, the filtrate was concentrated under reduced pressure. Precipitated crystals were collected by filtration to afford 46.8 g of 3-[3-amino-1-(4-fluorophenyl)-2,3-dihydro-5-methoxy-2-oxo-1H-indol-3-yl]propanenitrile. Melting point 136° to 138° C. EI-MS (m/z): 325 (M+).
COc1ccc2c(c1)C(N)(CCC#N)C(=O)N2c1ccc(F)cc1
null
null
null
822,895
ord_dataset-ec58fad8331a42c5a67ad75aac6713b4
null
2008-01-01T00:05:00
true
[CH2:1]([O:3][C:4]1[CH:5]=[C:6]([C:14]2[CH:19]=[C:18]([C:20]([F:23])([F:22])[F:21])[N:17]3[N:24]=[CH:25][C:26]([C:27]([OH:29])=O)=[C:16]3[N:15]=2)[CH:7]=[CH:8][C:9]=1[C:10]([F:13])([F:12])[F:11])[CH3:2].[NH2:30][C:31]1[CH:32]=[C:33]([S:37]([NH:40][CH2:41][CH3:42])(=[O:39])=[O:38])[CH:34]=[CH:35][CH:36]=1>>[CH2:41]([NH:40][S:37]([C:33]1[CH:32]=[C:31]([NH:30][C:27]([C:26]2[CH:25]=[N:24][N:17]3[C:18]([C:20]([F:22])([F:23])[F:21])=[CH:19][C:14]([C:6]4[CH:7]=[CH:8][C:9]([C:10]([F:12])([F:11])[F:13])=[C:4]([O:3][CH2:1][CH3:2])[CH:5]=4)=[N:15][C:16]=23)=[O:29])[CH:36]=[CH:35][CH:34]=1)(=[O:39])=[O:38])[CH3:42]
CCNS(=O)(=O)c1cccc(N)c1
CCOc1cc(-c2cc(C(F)(F)F)n3ncc(C(=O)O)c3n2)ccc1C(F)(F)F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared from 5-(3-ethoxy-4-trifluoromethyl-phenyl)-7-trifluoromethyl-pyrazolo[1,5-a]pyrimidine-3-carboxylic acid (example C.11) and 3-amino-N-ethyl-benzenesulfonamide [CAS 56445-08-0] according to general procedure II. Yellow solid. MS (ISP) 600.0 [(M−H)−]; mp 226° C.
CCNS(=O)(=O)c1cccc(NC(=O)c2cnn3c(C(F)(F)F)cc(-c4ccc(C(F)(F)F)c(OCC)c4)nc23)c1
null
null
null
222,302
ord_dataset-42629b4cf1094978a5e5f29f22639ee7
null
1991-01-01T00:01:00
true
C(O[C@H:5]1[C@H:10]([N:11]2[CH2:15][CH2:14][N:13]([CH3:16])[C:12]2=[N:17][C:18]#[N:19])[C:9]2[CH:20]=[C:21]([C:24]#[N:25])[CH:22]=[CH:23][C:8]=2[O:7][C:6]1([CH3:27])[CH3:26])(=O)C.N12CCCN=C1CCCCC2>C1(C)C=CC=CC=1>[C:18]([N:17]=[C:12]1[N:13]([CH3:16])[CH2:14][CH2:15][N:11]1[C:10]1[C:9]2[CH:20]=[C:21]([C:24]#[N:25])[CH:22]=[CH:23][C:8]=2[O:7][C:6]([CH3:27])([CH3:26])[CH:5]=1)#[N:19]
CC(=O)O[C@H]1[C@H](N2CCN(C)C2=NC#N)c2cc(C#N)ccc2OC1(C)C
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCC2=NCCCN2CC1
Cc1ccccc1
null
null
null
null
null
null
null
null
null
100
0.67
To a suspension of trans-3-acetoxy-4-(2-cyanoimino-3-methylimidazolidin-1-yl)-3,4-dihydro-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile (0.45 g) in toluene (9 ml) was added 1,8-diazabicyclo[5.4.0]undec-7-ene (0.23 ml), and the reaction mixture was stirred at 100° C. for 2 hours and 40 minutes. The solvent was removed under reduced pressure. The residue was poured into water (30 ml) and then extracted with ethyl acetate (45 ml). The organic layer was washed with brine (30 ml), dried over magnesium sulfate and evaporated in vacuo. The residue was recrystallized from ethanol to give 4-(2-cyanoimino-3-methylimidazolidin-1-yl)-2,2-dimethyl-2H-1-benzopyran-6-carbonitrile (0.27 g).
CN1CCN(C2=CC(C)(C)Oc3ccc(C#N)cc32)C1=NC#N
null
71.7
null
1,256,216
ord_dataset-266f60b4555945d6afb2d2bdf5fa04e0
null
2013-01-01T00:02:00
true
[NH:1]1[C:5]([C:6]2[CH:7]=[C:8]([C:12]3[C:13]([OH:18])=[CH:14][CH:15]=[CH:16][CH:17]=3)[CH:9]=[CH:10][CH:11]=2)=[N:4][N:3]=[N:2]1.[N+:19]([O-])([OH:21])=[O:20].O>C(O)C>[N+:19]([C:14]1[CH:15]=[CH:16][CH:17]=[C:12]([C:8]2[CH:9]=[CH:10][CH:11]=[C:6]([C:5]3[NH:1][N:2]=[N:3][N:4]=3)[CH:7]=2)[C:13]=1[OH:18])([O-:21])=[O:20]
Oc1ccccc1-c1cccc(-c2nnn[nH]2)c1
O=[N+]([O-])O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CCO
null
null
null
null
null
null
null
null
null
null
8
3′-(1H-Tetrazol-5-yl)-biphenyl-2-ol 8d (3.5 g, 14.7 mmol) was dissolved in 145 mL of ethanol under argon atmosphere. Fuming nitric acid (0.565 mL, 13.2 mmol) was added dropwise at 35° C. After the reaction mixture was reacted at room temperature for 1 hour, 150 mL of water was added. After standing overnight, the mixture was filtered. The filter cake was washed with 100 mL of water and dissolved in 500 mL of ethyl acetate and 250 mL of water. The separated organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The mixture was purified by silica gel column chromatography to obtain the title compound 3-nitro-3′-(1H-tetrazol-5-yl)-biphenyl-2-ol 8e (1 g, yield 27.0%) as a yellow solid.
O=[N+]([O-])c1cccc(-c2cccc(-c3nnn[nH]3)c2)c1O
null
26.7
null
629,368
ord_dataset-0a66204fc43e49c2922e6f9107e6b62f
null
2004-01-01T00:03:00
true
[CH:1]([C@H:4]1[O:9][CH2:8][C@H:7]([NH2:10])[CH2:6][O:5]1)([CH3:3])[CH3:2].Cl[C:12]1[C:21]2[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=2)[C:15]([CH2:22][C:23]2[CH:24]=[N:25][C:26]([OH:29])=[CH:27][CH:28]=2)=[CH:14][N:13]=1.C(N(CCCC)CCCC)CCC>CCOC(C)=O.C([O-])(O)=O.[Na+]>[CH:1]([C@H:4]1[O:9][CH2:8][C@H:7]([NH:10][C:12]2[C:21]3[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=3)[C:15]([CH2:22][C:23]3[CH:24]=[N:25][C:26]([OH:29])=[CH:27][CH:28]=3)=[CH:14][N:13]=2)[CH2:6][O:5]1)([CH3:3])[CH3:2]
CC(C)[C@H]1OC[C@H](N)CO1
Oc1ccc(Cc2cnc(Cl)c3ccccc23)cn1
null
O=C([O-])O
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCCCN(CCCC)CCCC
CCOC(C)=O
null
null
null
null
null
null
null
null
null
null
null
In a sealed glass bottle under N2-atmosphere, 424 mg (2.92 mmol) of trans 2-isopropyl-[1,3]dioxan-5-ylamine, 396 mg (1.46 mmol) of 1-chloro-4-[(6-hydroxy-pyridin-3-yl)methyl]-isoquinoline (contains 1-iodo derivative) and 2 ml of tributylamine are stirred at 150° C. for 48 h. The resulting mixture is diluted with EtOAc and NaHCO3-solution, the aqueous layer is separated and extracted twice with EtOAc. The organic phases are washed with brine, dried (Na2SO4) and concentrated in vaccuo. “Reversed Phase” medium-pressure chromatography (water/acetonitrile/TFA) yields trans 1-(2-isopropyl-[1,3]dioxan-5-ylamino)-4-[(6-hydroxy-pyridin-3-yl)methyl]-isoquinoline; FAB-MS; (M+H)+=286; HPLC(gradient20-100) tRet=8.6.
CC(C)[C@H]1OC[C@H](Nc2ncc(Cc3ccc(O)nc3)c3ccccc23)CO1
null
null
null
165,227
ord_dataset-12ef86aced0149e0917be82ce22190e2
null
1987-01-01T00:11:00
true
[CH3:1][C:2]1[NH:3][C:4]([CH3:36])=[C:5]([C:32]([O:34][CH3:35])=[O:33])[CH:6]([C:23]2[CH:28]=[CH:27][CH:26]=[C:25]([N+:29]([O-:31])=[O:30])[CH:24]=2)[C:7]=1[C:8]1[O:12][N:11]=[C:10]([CH2:13][S:14]([CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[O:15])[N:9]=1.ClC1C=C(C=CC=1)C(OO)=[O:42]>C(Cl)(Cl)Cl>[CH3:1][C:2]1[NH:3][C:4]([CH3:36])=[C:5]([C:32]([O:34][CH3:35])=[O:33])[CH:6]([C:23]2[CH:28]=[CH:27][CH:26]=[C:25]([N+:29]([O-:31])=[O:30])[CH:24]=2)[C:7]=1[C:8]1[O:12][N:11]=[C:10]([CH2:13][S:14]([CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)(=[O:42])=[O:15])[N:9]=1
O=C(OO)c1cccc(Cl)c1
COC(=O)C1=C(C)NC(C)=C(c2nc(CS(=O)Cc3ccccc3)no2)C1c1cccc([N+](=O)[O-])c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)Cl
null
null
null
null
null
null
null
null
null
null
25
8
To a solution of 550 mg of methyl 1,4-dihydro-2,6-dimethyl-3-(3-benzylsulfinylmethyl-1,2,4-oxadiazol-5-yl)-4-(3-nitrophenyl)pyridine-5-carboxylate in 30 ml of chloroform was added 520 mg of m-chloroperoxybenzoic acid. After stirring at room temperature for 8 hours, the mixture was treated in the same manner as described in Example 117 to give 180 mg of methyl 1,4-dihydro-2,6-dimethyl-3-(3-benzylsulfonylmethyl-1,2,4-oxadiazol-5-yl)-4-(3-nitrophenyl)pyridine-5-carboxylate, m.p. 227° C.
COC(=O)C1=C(C)NC(C)=C(c2nc(CS(=O)(=O)Cc3ccccc3)no2)C1c1cccc([N+](=O)[O-])c1
null
31.7
null
1,247,833
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
null
2013-01-01T00:01:00
true
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[N:12]([C:13]3[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:14]=3[Cl:20])[N:11]=[C:10]([C:21](O)=O)[C:9]=2[CH3:24])=[CH:4][CH:3]=1.[CH2:25]([NH:32][C:33]([CH3:38])([CH3:37])[C:34]([NH2:36])=[O:35])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1>>[CH2:25]([N:32]1[C:33]([CH3:37])([CH3:38])[C:34](=[O:35])[N:36]=[C:21]1[C:10]1[C:9]([CH3:24])=[C:8]([C:5]2[CH:4]=[CH:3][C:2]([Cl:1])=[CH:7][CH:6]=2)[N:12]([C:13]2[CH:18]=[CH:17][C:16]([Cl:19])=[CH:15][C:14]=2[Cl:20])[N:11]=1)[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1
Cc1c(C(=O)O)nn(-c2ccc(Cl)cc2Cl)c1-c1ccc(Cl)cc1
CC(C)(NCc1ccccc1)C(N)=O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Compound 13 was synthesized from 4a (250 mg, 0.66 mmol) and 5h (189 mg, 0.99 mmol) as a white solid (152 mg, 43%) in a manner similar to that described in Example 36. 1H NMR (400 MHz, CDCl3) δ 7.38 (d, 1H), 7.31 (d, 2H), 7.26 (m, 5H), 7.20 (dd, 1H), 7.04 (d, 2H), 7.01 (d, 1H), 5.29 (s, 2H), 2.45 (s, 3H), 1.31 (s, 6H); ESMS m/z: 537.1 (M+1).
Cc1c(C2=NC(=O)C(C)(C)N2Cc2ccccc2)nn(-c2ccc(Cl)cc2Cl)c1-c1ccc(Cl)cc1
null
null
null
562,209
ord_dataset-7c28974b7fcf4c9c86d5f2a42ba328a2
null
2002-01-01T00:09:00
true
[OH-].[Na+].O.[CH3:4][C:5]1[CH:6]=[C:7]2[C:11](=[CH:12][CH:13]=1)[NH:10][C:9]1[CH2:14][C:15]3[C:20]([C:8]2=1)=[CH:19][CH:18]=[CH:17][CH:16]=3.[CH3:21]I>C1C=CC=CC=1>[CH3:21][N:10]1[C:11]2[C:7](=[CH:6][C:5]([CH3:4])=[CH:13][CH:12]=2)[C:8]2[C:20]3[C:15]([CH2:14][C:9]1=2)=[CH:16][CH:17]=[CH:18][CH:19]=3
Cc1ccc2[nH]c3c(c2c1)-c1ccccc1C3
CI
null
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
c1ccccc1
null
null
null
null
null
null
null
null
null
25
2
45 g of NaOH, 60 ml of water, 60 ml of benzene, 0.3 g of trimethyl-cethyl-ammonium bromide, 19.3(0.088 mol) of 2-methyl-5,6-dihydroindeno[2,1-b]indole, prepared in Example 8-bis, and 7.5 ml (0.12 mol) of CH3I were placed in a bulb. The resulting two-phase system was stirred for 2 hours at room temperature and then 10 minutes at reflux. Then the reaction mixture cooled to room temperature and filtered. The obtained precipitate was washed twice with ethanol and finally dried, thus obtaining 18 g of N-methyl-2-methyl-5,6-dihydroindeno[2,1-b]indole (yield=88%).
Cc1ccc2c(c1)c1c(n2C)Cc2ccccc2-1
null
88
null
1,347,633
ord_dataset-6034127657614f02860ed057b62b882e
null
2013-01-01T00:10:00
true
Cl[C:2]1[C:7]([C:8]([NH:10][CH2:11][C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([F:18])[CH:13]=2)=[O:9])=[C:6]([CH3:19])[CH:5]=[C:4]([N:20]2[CH2:25][CH2:24][O:23][CH2:22][CH2:21]2)[N:3]=1.[CH:26](/B(O)O)=[CH:27]\[CH3:28].CCO>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[F:18][C:14]1[CH:13]=[C:12]([CH:17]=[CH:16][CH:15]=1)[CH2:11][NH:10][C:8]([C:7]1[C:2](/[CH:26]=[CH:27]/[CH3:28])=[N:3][C:4]([N:20]2[CH2:25][CH2:24][O:23][CH2:22][CH2:21]2)=[CH:5][C:6]=1[CH3:19])=[O:9]
C/C=C/B(O)O
Cc1cc(N2CCOCC2)nc(Cl)c1C(=O)NCc1cccc(F)c1
null
c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
CCO
null
null
null
null
null
null
null
null
null
110
null
To a solution of 400 mg (1.1 mmol) 2-chloro-N-[(3-fluorophenyl)-methyl]-4-methyl-6-morpholin-4-yl-pyridine-3-carboxylic acid amide in toluene (15 ml) were added 140 mg (1.7 mmol) (E)-prop-1-enylboronic acid, 1.1 g (3.3 mmol) CsCO3 and EtOH (1.5 ml). After degassing with argon for 15 min 370 mg (0.32 mmol) Pd(PPh3)4 were added and the RM was heated to 110° C. for 5 h. Subsequently the RM was filtered through celite and the filtrate was concentrated in vacuo. Purification of the residue by CC (hexane/EtOAc 3:1) provided 300 mg (0.8 mmol, 74%) (E)-N-(3-fluorobenzyl)-4-methyl-6-morpholino-2-(prop-1-enyl)-pyridine-3-carboxylic acid amide (example 9). [M+H]+ 370.2.
C/C=C/c1nc(N2CCOCC2)cc(C)c1C(=O)NCc1cccc(F)c1
null
72.7
null
1,397,211
ord_dataset-12dc3bd21bcf44d09e5b4249afe15161
null
2014-01-01T00:02:00
true
[F:1][C:2]1[CH:3]=[C:4]([NH:9][C:10]2[CH:15]=[CH:14][C:13]([F:16])=[CH:12][N:11]=2)[C:5]([NH2:8])=[CH:6][CH:7]=1.[C:17]([O:21][C:22]([NH:24][C@@H:25]([CH3:29])[C:26](O)=[O:27])=[O:23])([CH3:20])([CH3:19])[CH3:18].C1C=NC2N(O)N=NC=2C=1.Cl.CN(C)CCCN=C=NCC>C(Cl)Cl>[C:17]([O:21][C:22](=[O:23])[NH:24][C@H:25]([C:26](=[O:27])[NH:8][C:5]1[CH:6]=[CH:7][C:2]([F:1])=[CH:3][C:4]=1[NH:9][C:10]1[CH:15]=[CH:14][C:13]([F:16])=[CH:12][N:11]=1)[CH3:29])([CH3:18])([CH3:19])[CH3:20]
C[C@H](NC(=O)OC(C)(C)C)C(=O)O
Nc1ccc(F)cc1Nc1ccc(F)cn1
null
CCN=C=NCCCN(C)C
Cl
On1nnc2cccnc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
null
null
null
null
null
null
null
null
null
null
0
1
A mixture of 4-fluoro-N2-(5-fluoropyridin-2-yl)benzene-1,2-diamine (30 mg, 0.136 mmol), (S)-2-tertbutoxycarbonylaminopropionic acid (28 mg, 0.15 mmol), HOAt (20 mg, 0.15 mmol) and N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (29 mg, 0.15 mmol) in DCM (5 mL) was stirred at 0° C. for 1 h. Additional (S)-2-tertbutoxycarbonylaminopropionic acid (5 mg), HOAt (4 mg) and N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (5 mg) were added and stirring continued for 30 min. The reaction mixture was partitioned between DCM and a saturated aqueous solution of NaHCO3. The organic layer was dried and concentrated in vacuo to afford {(S)-1-[4-fluoro-2-(5-fluoropyridin-2-ylamino)phenylcarbamoyl]ethyl}carbamic acid tert-butyl ester as an orange oil. LCMS (Method C): RT 3.51 min [M+H]+ 393.1.
C[C@H](NC(=O)OC(C)(C)C)C(=O)Nc1ccc(F)cc1Nc1ccc(F)cn1
null
null
null
1,436,657
ord_dataset-275a3da8f45f4536ad29727f0ef9ba66
null
2014-01-01T00:06:00
true
C(=O)([O-])[O-].[Cs+].[Cs+].[Br:7][C:8]1[CH:9]=[C:10]2[C:14](=[CH:15][CH:16]=1)[NH:13][CH:12]=[C:11]2[CH:17]=[O:18].I[CH:20]([CH3:22])[CH3:21]>CN(C=O)C>[Br:7][C:8]1[CH:9]=[C:10]2[C:14](=[CH:15][CH:16]=1)[N:13]([CH:20]([CH3:22])[CH3:21])[CH:12]=[C:11]2[CH:17]=[O:18]
CC(C)I
O=Cc1c[nH]c2ccc(Br)cc12
null
O=C([O-])[O-]
[Cs+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
25
0.25
Cesium carbonate (545 mg, 1.67 mmol) was added to a stirred room temperature of 5-bromo-1H-indole-3-carbaldehyde (125 mg, 0.56 mmol) in DMF (1.0 mL) and the mixture was stirred at room temperature for 15 minutes. Then 2-iodopropane (0.112 mL, 1.116 mmol) was added and the solution was stirred at 80° C. for 2 hours. The solvent was removed under reduced pressure and the residue was partitioned between ethyl acetate (2×20 mL) and saturated sodium bicarbonate (5 mL), washed with brine (10 mL), dried over sodium sulfate, filtered and concentrated under reduced pressure to give the title compound (148 mg).
CC(C)n1cc(C=O)c2cc(Br)ccc21
null
99.3
null
822,085
ord_dataset-ec58fad8331a42c5a67ad75aac6713b4
null
2008-01-01T00:05:00
true
[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@H:6]1[O:24][C:25]1[C:29]([CH2:30][C:31]2[CH:36]=[CH:35][C:34](/[CH:37]=[CH:38]/[CH2:39][C:40](O)=[O:41])=[CH:33][CH:32]=2)=[C:28]([CH:43]([CH3:45])[CH3:44])[NH:27][N:26]=1)(=[O:3])[CH3:2].ON1C2C=CC=CC=2N=N1.Cl.C(N=C=NCCCN(C)C)C.[NH2:68][C@@H:69]([CH3:80])[C:70]([O:72][CH2:73][C:74]1[CH:79]=[CH:78][CH:77]=[CH:76][CH:75]=1)=[O:71]>CN(C)C=O.O>[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@H:6]1[O:24][C:25]1[C:29]([CH2:30][C:31]2[CH:32]=[CH:33][C:34](/[CH:37]=[CH:38]/[CH2:39][C:40](=[O:41])[NH:68][C@H:69]([C:70]([O:72][CH2:73][C:74]3[CH:79]=[CH:78][CH:77]=[CH:76][CH:75]=3)=[O:71])[CH3:80])=[CH:35][CH:36]=2)=[C:28]([CH:43]([CH3:45])[CH3:44])[NH:27][N:26]=1)(=[O:3])[CH3:2]
CC(=O)OC[C@H]1O[C@@H](Oc2n[nH]c(C(C)C)c2Cc2ccc(/C=C/CC(=O)O)cc2)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O
C[C@H](N)C(=O)OCc1ccccc1
null
CCN=C=NCCCN(C)C
Cl
On1nnc2ccccc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CN(C)C=O
null
null
null
null
null
null
null
null
null
25
8
To a solution of 3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)-4-({4-[(1E)-3-carboxyprop-1-enyl]phenyl}methyl)-5-isopropyl-1H-pyrazole (7.13 g) in N,N-dimethylformamide (30 mL) were added 1-hydroxybenzotriazole (2.31 g), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (3.25 g) and benzyl (S)-2-aminopropionate (8.34 g), and the mixture was stirred at room temperature overnight. The reaction mixture was poured into water, and the resulting mixture was extracted with ethyl acetate twice. The extracts were washed with water and brine successively, and dried over sodium sulfate. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=1/2) to give 3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)-4-[(4-{(1E)-3-[(S)-1-(benzyloxycarbonyl)ethylcarbamoyl]prop-1-enyl}phenyl)methyl]-5-isopropyl-1H-pyrazole (3.25 g). This material was dissolved in methanol (40 mL). To the solution was added 10% palladium-carbon powder (1.0 g), and the mixture was stirred at room temperature under a hydrogen atmosphere overnight. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure to give 3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)-4-[(4-{3-[(S)-1-(carboxy)ethylcarbamoyl]propyl}phenyl)methyl]-5-isopropyl-1H-pyrazole (2.25 g). To a solution of the obtained 3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)-4-[(4-{3-[(S)-1-(carboxy)ethylcarbamoyl]propyl}phenyl)methyl]-5-isopropyl-1H-pyrazole (0.09 g) in N,N-dimethylformamide (0.5 mL) were added 1-hydroxybenzotriazole (0.026 g), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (0.037 g) and 2-amino-1,3-propanediol (0.12 g), and the mixture was stirred at room temperature for 1 hour. To the reaction mixture was added 5 mol/L aqueous sodium hydroxide solution (0.5 mL), and the mixture was stirred at room temperature for 1 hour. Acetic acid (0.3 mL) and water (1 mL) were added to the reaction mixture. The insoluble material was removed by filtration, and the filtrate was purified by preparative reverse phase column chromatography (Shiseido CAPCELL PAK UG120 ODS, 5 μL, 120 Å, 20×50 mm, flow rate 30 mL/minute linear gradient, water/acetonitrile=90/10-10/90) to give the title compound (0.017 g).
CC(=O)OC[C@H]1O[C@@H](Oc2n[nH]c(C(C)C)c2Cc2ccc(/C=C/CC(=O)N[C@@H](C)C(=O)OCc3ccccc3)cc2)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O
null
36.3
null
894,397
ord_dataset-11068b1e475b4c5b82e56726ab0dddb7
null
2009-01-01T00:07:00
true
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([F:11])([F:10])[F:9])=[CH:4][C:3]=1[N:12]=[C:13]=[O:14].[NH2:15][C:16]1[CH:21]=[CH:20][C:19]([C:22]2[C:26]3=[N:27][CH:28]=[CH:29][CH:30]=[C:25]3[NH:24][C:23]=2[C:31]([NH2:33])=[O:32])=[CH:18][CH:17]=1>O1CCCC1>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([F:11])([F:10])[F:9])=[CH:4][C:3]=1[NH:12][C:13](=[O:14])[NH:15][C:16]1[CH:17]=[CH:18][C:19]([C:22]2[C:26]3=[N:27][CH:28]=[CH:29][CH:30]=[C:25]3[NH:24][C:23]=2[C:31]([NH2:33])=[O:32])=[CH:20][CH:21]=1
NC(=O)c1[nH]c2cccnc2c1-c1ccc(N)cc1
O=C=Nc1cc(C(F)(F)F)ccc1F
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1CCOC1
null
null
null
null
null
null
null
null
null
null
null
1
73 mg of 2-fluoro-5-trifluoromethylphenyl isocyanate are added to a solution of 80 mg of 3-(4-aminophenyl)-1H-pyrrolo[3,2-b]pyridine-2-carboxamide in 18 ml of tetrahydrofuran. After stirring for 1 hour, the mixture is concentrated under reduced pressure and the residue is purified by chromatography on a silica column, elution being carried out with a mixture of cyclohexane and ethyl acetate (20/80 by volume) to give 110 mg of 3-{4-[3-(2-fluoro-5-trifluoromethylphenyl)-ureido]phenyl}-1H-pyrrolo[3,2-b]pyridine-2-carboxamide, the characteristics of which are as follows:
NC(=O)c1[nH]c2cccnc2c1-c1ccc(NC(=O)Nc2cc(C(F)(F)F)ccc2F)cc1
null
75.8
null
1,386,616
ord_dataset-31641fb65b34430fa7435229b949b604
null
2014-01-01T00:01:00
true
[CH3:1][O:2][CH2:3][CH2:4][CH2:5][OH:6].[N+:7]([C:10]1[CH:17]=[CH:16][CH:15]=[C:14]([N+]([O-])=O)[C:11]=1[C:12]#[N:13])([O-:9])=[O:8]>>[CH3:1][O:2][CH2:3][CH2:4][CH2:5][O:6][C:14]1[CH:15]=[CH:16][CH:17]=[C:10]([N+:7]([O-:9])=[O:8])[C:11]=1[C:12]#[N:13]
N#Cc1c([N+](=O)[O-])cccc1[N+](=O)[O-]
COCCCO
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Prepared as in Example 111c from 3-methoxypropan-1-ol and 2,6-dinitrobenzonitrile in 63.6% yield. 1H NMR (400 MHz, CDCl3) δ 2.16 (m, 2H), 3.36 (s, 3H), 3.63 (t, J=5.6 Hz, 2H), 4.29 (t, J=6.4 Hz, 2H), 7.35 (dd, J=8.8, 0.8 Hz, 1H), 7.69 (t, J=8.8 Hz, 1H), (dd, J=8.4, 0.8 Hz, 1H).
COCCCOc1cccc([N+](=O)[O-])c1C#N
null
63.6
null
1,751,437
ord_dataset-97eb2ab57fec4160922caae33b54d956
null
2016-01-01T00:08:00
true
C[O:2][C:3]([C@@H:5]1[CH2:9][C@H:8]([NH:10][C:11]([C:13]2[CH:22]=[CH:21][C:20]3[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=3)[C:14]=2[OH:23])=[O:12])[CH2:7][N:6]1[CH2:24][CH:25]1[CH2:30][CH2:29][CH2:28][CH2:27][CH2:26]1)=[O:4].[OH-].[Li+].Cl>CO>[CH:25]1([CH2:24][N:6]2[CH2:7][C@@H:8]([NH:10][C:11]([C:13]3[CH:22]=[CH:21][C:20]4[C:15](=[CH:16][CH:17]=[CH:18][CH:19]=4)[C:14]=3[OH:23])=[O:12])[CH2:9][C@H:5]2[C:3]([OH:4])=[O:2])[CH2:30][CH2:29][CH2:28][CH2:27][CH2:26]1
COC(=O)[C@@H]1C[C@H](NC(=O)c2ccc3ccccc3c2O)CN1CC1CCCCC1
null
null
Cl
[Li+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
null
24
To a stirred solution of (2S,4S)-1-cyclohexylmethyl-4-[(1-hydroxy-naphthalene-2-carbonyl)-amino]-pyrrolidine-2-carboxylic acid methyl ester (350 mg, 0.85 mmol) in methanol (8 mL) was added lithium hydroxide (204 mg, 8.53 mmol) and the mixture was stirred at room temp. for 24 h. The reaction mixture was then acidified with dilute hydrochloric acid, extracted with ethyl acetate and washed with water and brine. The organic layer was dried over anhydrous sodium sulfate, filtered, concentrated and purified by column chromatography (using 15% EtOAc in hexane as eluent) to give (2S,4S)-1-cyclohexylmethyl-4-[(1-hydroxy-naphthalene-2-carbonyl)-amino]-pyrrolidine-2-carboxylic acid (250 mg, 74.0% yield) as a white solid. MS caled. for C23H29N2O4[(M+H)+] 397.0, obsd. 397.6.
O=C(N[C@H]1C[C@@H](C(=O)O)N(CC2CCCCC2)C1)c1ccc2ccccc2c1O
null
74.2
null
484,003
ord_dataset-cb5c1a9eddff4790b1bd650617c32d34
null
2000-01-01T00:11:00
true
[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[CH2:13][CH2:12][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:10][CH:9]2[OH:21])=[CH:4][CH:3]=1.Br[CH2:23][C:24]1[CH:33]=[CH:32][C:31]2[C:26](=[CH:27][CH:28]=[CH:29][CH:30]=2)[C:25]=1[O:34][CH3:35]>>[F:1][C:2]1[CH:3]=[CH:4][C:5]([CH:8]2[CH2:13][CH2:12][N:11]([C:14]([O:16][C:17]([CH3:18])([CH3:20])[CH3:19])=[O:15])[CH2:10][CH:9]2[O:21][CH2:23][C:24]2[CH:33]=[CH:32][C:31]3[C:26](=[CH:27][CH:28]=[CH:29][CH:30]=3)[C:25]=2[O:34][CH3:35])=[CH:6][CH:7]=1
CC(C)(C)OC(=O)N1CCC(c2ccc(F)cc2)C(O)C1
COc1c(CBr)ccc2ccccc12
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
In an analogous manner to that described in Example 3(c), by alkylating tert-butyl (3RS,4RS)-4-(4-fluorophenyl)-3-hydroxy-piperidine-1-carboxylate [Example 3(b)] with 2-bromomethyl-1-methoxy-naphthalene there was obtained tert-butyl (3RS,4RS)-4-(4-fluorophenyl)-3-[1-methoxy-naphthalen-2-yl-methoxy]-piperidine-1-carboxylate as a colourless resin; MS: 465 (M)+.
COc1c(COC2CN(C(=O)OC(C)(C)C)CCC2c2ccc(F)cc2)ccc2ccccc12
null
null
null
182,918
ord_dataset-f25e1b7f8ef54305a5170f5395a768c7
null
1989-01-01T00:01:00
true
[CH3:1][C:2]1[NH:3][C:4](=[O:22])[CH2:5][S:6][C:7]=1[CH:8]1[CH:13]=[CH:12][N:11](C(OCC(Cl)(Cl)Cl)=O)[N:10]=[CH:9]1.[S]>>[CH3:1][C:2]1[NH:3][C:4](=[O:22])[CH2:5][S:6][C:7]=1[C:8]1[CH:13]=[CH:12][N:11]=[N:10][CH:9]=1
CC1=C(C2C=CN(C(=O)OCC(Cl)(Cl)Cl)N=C2)SCC(=O)N1
null
null
[S]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
140
1.5
5-methyl-6-[1-(2,2,2-trichloroethoxycarbonyl)-1,4-dihydro-4-pyridazinyl]-2H-1,4-thiazin-3(4H)-one (2.4 g) was well mixed with sulfur sublimed (10.7 g) in a mortar and the mixture was stirred at 140° C. for 1.5 hours and then was cooled to ambient temperature. The obtained solid was ground and was extracted with methanol. Methanol was removed under reduced pressure. The residue was dissolved in 50 ml of 2N hydrochloric acid. The insoluble matter was removed by filtration and the filtrate was adjusted to pH 7.2 by 2N aqueous sodium hydroxide. The resulting precipitates were removed by filtration. The filtrate was extracted with chloroform (20 ml×5 times) and the extract was evaporated to dryness. After combined with the above solid, the residue was recrystallized from methanol to give the titled compound (0.3 g, yield 23%) as pale yellow plates.
CC1=C(c2ccnnc2)SCC(=O)N1
null
23.2
null
1,664,052
ord_dataset-42cd9bc5aae3485f9a58f1527bd3abf0
null
2015-01-01T00:11:00
true
Br[C:2]1[C:10]2[CH:11]=[C:12]3[C:20]([C:21]([CH3:23])([CH3:22])[C:9]=2[C:8]2[C:3]=1[CH:4]=[CH:5][CH:6]([C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1)[CH:7]=2)=[C:19]1[C:14]([CH:15]=[CH:16][CH:17]=[CH:18]1)=[N:13]3.[C:30]1(C2C=CC=CC=2)[CH:35]=[CH:34][C:33]([N:36](C2C=CC(B3OC(C)(C)C(C)(C)O3)=CC=2)[C:37]2[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=2)=[CH:32][CH:31]=1.C(=O)([O-])[O-].[K+].[K+]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1(C)C=CC=CC=1.C(O)C>[C:6]1([C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)[CH:7]=[CH:8][C:3]([N:36]([C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][CH:42]=2)[C:33]2[CH:32]=[CH:31][C:30]([C:2]3[C:10]4[CH:11]=[C:12]5[C:20]([C:21]([CH3:23])([CH3:22])[C:9]=4[C:8]4[C:3]=3[CH:4]=[CH:5][CH:6]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[CH:7]=4)=[C:19]3[C:14]([CH:15]=[CH:16][CH:17]=[CH:18]3)=[N:13]5)=[CH:35][CH:34]=2)=[CH:4][CH:5]=1
CC1(C)OB(c2ccc(N(c3ccccc3)c3ccc(-c4ccccc4)cc3)cc2)OC1(C)C
CC1(C)C2=C(C=C3N=c4ccccc4=C31)C(Br)=C1C=CC(c3ccccc3)C=C12
null
c1ccc([P](c2ccccc2)(c2ccccc2)[Pd]([P](c2ccccc2)(c2ccccc2)c2ccccc2)([P](c2ccccc2)(c2ccccc2)c2ccccc2)[P](c2ccccc2)(c2ccccc2)c2ccccc2)cc1
O=C([O-])[O-]
[K+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
Cc1ccccc1
null
null
null
null
null
null
null
null
null
73
8
7-Bromo-12,12-dimethyl-10-phenyl-10,12-dihydro-indeno[2,1-b]carbazole synthesized in Example 1 (3.0 g), (biphenyl-4-yl)-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)phenyl]-phenylamine (3.7 g), a toluene/ethanol (4/1, v/v) mixed solvent (50 ml), and a 2M potassium carbonate aqueous solution (10 ml) were added to a nitrogen-substituted reaction vessel and aerated with nitrogen gas for 30 min under ultrasonic irradiation. The mixture was heated after adding tetrakis(triphenylphosphine)palladium (0.4 g), and stirred at 73° C. for 8 hours. After the mixture was cooled to a room temperature, a precipitated crude product was collected by filtration. 1,2-Dichlorobenzene (140 ml) was added to the crude product, and the crude product was dissolved while being heated, and after removing insoluble matter by filtration, a filtrate was concentrated under reduced pressure. Purification by recrystallization using 1,2-dichlorobenzene (100 ml) was performed to obtain a white powder of 7-[4-{(biphenyl-4-yl)-phenylamino}-phenyl]-12,12-dimethyl-10-phenyl-10,12-dihydroindeno[2,1-b]carbazole (2.7 g; yield 57.8%).
CC1(C)C2=C(C=C3N=c4ccccc4=C31)C(c1ccc(N(c3ccccc3)c3ccc(-c4ccccc4)cc3)cc1)=C1C=CC(c3ccccc3)C=C12
null
116.2
null
1,769,416
ord_dataset-0b32b90cc77b4a3db47ad263e0bbc1a8
null
2016-01-01T00:09:00
true
Cl[CH2:2][C:3]1[C:4]([S:10][CH:11]2[CH2:15][CH2:14][CH2:13]C2)=[N:5][C:6](C)=[CH:7][CH:8]=1.C([O:18][C:19]([CH:21]1[CH2:23][CH:22]1[C:24]1[CH:29]=[C:28]([F:30])[C:27]([OH:31])=[C:26]([F:32])[CH:25]=1)=[O:20])C>>[CH:11]1([S:10][C:4]2[C:3]([CH2:2][O:31][C:27]3[C:26]([F:32])=[CH:25][C:24]([CH:22]4[CH2:23][CH:21]4[C:19]([OH:20])=[O:18])=[CH:29][C:28]=3[F:30])=[CH:8][CH:7]=[CH:6][N:5]=2)[CH2:15][CH2:14][CH2:13]1
CCOC(=O)C1CC1c1cc(F)c(O)c(F)c1
Cc1ccc(CCl)c(SC2CCCC2)n1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
3-Chloromethyl-2-cyclobutylsulfanyl-pyridine (0.024 g, 0.113 mmol) obtained in Step C of Preparation Example 23 and 2-(3,5-difluoro-4-hydroxy-phenyl)-cyclopropane carboxylic acid ethyl ester (0.026 g, 0.113 mmol) obtained in Step B of Preparation Example 31 were used to react sequentially in the same manner as in Steps A and B of Example 1 to obtain the title compound (0.036 g, 81%).
O=C(O)C1CC1c1cc(F)c(OCc2cccnc2SC2CCC2)c(F)c1
null
81.4
null
1,460,022
ord_dataset-a86112d52cd54525a5e36d41f18aced2
null
2014-01-01T00:07:00
true
COC1C=CC(C[N:8]2[C:12]3=[N:13][CH:14]=[C:15]([C:17]4[CH:18]=[C:19]([NH:23][C:24](=[O:26])[CH3:25])[CH:20]=[CH:21][CH:22]=4)[CH:16]=[C:11]3[C:10]([CH3:27])=[N:9]2)=CC=1.FC(F)(F)C(O)=O>C(Cl)(Cl)Cl>[CH3:27][C:10]1[C:11]2[C:12](=[N:13][CH:14]=[C:15]([C:17]3[CH:18]=[C:19]([NH:23][C:24](=[O:26])[CH3:25])[CH:20]=[CH:21][CH:22]=3)[CH:16]=2)[NH:8][N:9]=1
COc1ccc(Cn2nc(C)c3cc(-c4cccc(NC(C)=O)c4)cnc32)cc1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClC(Cl)Cl
O=C(O)C(F)(F)F
null
null
null
null
null
null
null
null
null
50
null
To a solution of N-(3-(1-(4-methoxybenzyl)-3-methyl-1H-pyrazolo[3,4-b]pyridin-5-yl)phenyl)acetamide (113) (50 mg, 0.129 mmol) dissolved in chloroform (10 mL) was added trifluoroacetic acid (5 mL) and the reaction mixture was heated at 50° C. for 12 h. After completion of the reaction the solvents were removed and diluted with cold water, pH was adjusted to 8 and the aqueous phase extracted with chloroform two times. The organic layer was washed with brine solution and dried over sodium sulphate and the solvents were removed. The crude was passed through 100-200 mesh silica gel eluting the compound at 40% ethyl acetate in hexane as pale yellow solid N-(3-(3-methyl-1H-pyrazolo[3,4-b]pyridin-5-yl)phenyl)acetamide 114 (30 mg). MS m/z 266.9 (M+H)+.
CC(=O)Nc1cccc(-c2cnc3[nH]nc(C)c3c2)c1
null
null
null
1,657,670
ord_dataset-42cd9bc5aae3485f9a58f1527bd3abf0
null
2015-01-01T00:11:00
true
C([O:8][C:9]1[CH:10]=[C:11]([C:15]2[CH:16]=[C:17]3[C:22](=[N:23][CH:24]=2)[N:21]([C:25]([NH2:27])=[O:26])[CH2:20][CH2:19][CH2:18]3)[CH:12]=[N:13][CH:14]=1)C1C=CC=CC=1>CCO.[Pd]>[OH:8][C:9]1[CH:10]=[C:11]([C:15]2[CH:16]=[C:17]3[C:22](=[N:23][CH:24]=2)[N:21]([C:25]([NH2:27])=[O:26])[CH2:20][CH2:19][CH2:18]3)[CH:12]=[N:13][CH:14]=1
NC(=O)N1CCCc2cc(-c3cncc(OCc4ccccc4)c3)cnc21
null
null
[Pd]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
null
null
A stirred suspension of 6-(5-benzyloxy-pyridin-3-yl)-3,4-dihydro-2H-[1,8]naphthyridine-1-carboxylic acid amide (167 mg, 0.46 mmol) in EtOH (10 mL) is hydrogenated over 10% palladium on carbon (17 mg) under balloon pressure for 16 h. The catalyst is removed by filtration through diatomaceous earth, washing well with DCM. The solvent is evaporated to afford the title compound (125 mg).
NC(=O)N1CCCc2cc(-c3cncc(O)c3)cnc21
null
100.5
null
1,235,159
ord_dataset-e96f5a2842f14e5380461c234100f05a
null
2012-01-01T00:12:00
true
C(O)C.[O:4]1[C:9]2[CH:10]=[CH:11][C:12]([CH2:14][NH:15][CH:16]3[CH2:21][CH2:20][N:19]([CH2:22][CH2:23][N:24]4[C:33]5[C:28](=[CH:29][CH:30]=[C:31]([O:34][CH3:35])[CH:32]=5)[C:27](/[CH:36]=[CH:37]/[C:38]([O:40]CC)=[O:39])=[CH:26][C:25]4=[O:43])[CH2:18][CH2:17]3)=[CH:13][C:8]=2[O:7][CH2:6][CH2:5]1.[OH-].[Na+]>O>[O:4]1[C:9]2[CH:10]=[CH:11][C:12]([CH2:14][NH:15][CH:16]3[CH2:17][CH2:18][N:19]([CH2:22][CH2:23][N:24]4[C:33]5[C:28](=[CH:29][CH:30]=[C:31]([O:34][CH3:35])[CH:32]=5)[C:27](/[CH:36]=[CH:37]/[C:38]([OH:40])=[O:39])=[CH:26][C:25]4=[O:43])[CH2:20][CH2:21]3)=[CH:13][C:8]=2[O:7][CH2:6][CH2:5]1
CCOC(=O)/C=C/c1cc(=O)n(CCN2CCC(NCc3ccc4c(c3)OCCO4)CC2)c2cc(OC)ccc12
null
null
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
O
null
null
null
null
null
null
null
null
null
null
1
To 1 mL of an ethanol solution containing 65 mg of ethyl(2E)-3-(1-(2-(4-((2,3-dihydro-1,4-benzodioxin-6-ylmethyl)amino)piperidin-1-yl)ethyl)-7-methoxy-2-oxo-1,2-dihydroquinolin-4-yl)acrylate, 0.2 mL of water and 0.11 mL of 5 mol/L aqueous sodium hydroxide solution were added and stirred for 1 hour. 2 mL of water was added, removed ethanol under reduced pressure, adjusted to pH 6.0 with 1 mol/L hydrochloric acid, and the resulting solid was filtered to afford 48 mg of (2E)-3-(1-(2-(4-((2,3-dihydro-1,4-benzodioxin-6-ylmethyl)amino)piperidin-1-yl)ethyl)-7-methoxy-2-oxo-1,2-dihydroquinolin-4-yl)acrylic acid as a yellow solid.
COc1ccc2c(/C=C/C(=O)O)cc(=O)n(CCN3CCC(NCc4ccc5c(c4)OCCO5)CC3)c2c1
null
77.8
null
1,523,287
ord_dataset-8c74302143c04eb9983e4b3a7ead2d72
null
2014-01-01T00:12:00
true
CN(/[CH:4]=[C:5]1\[CH2:6][CH2:7][CH2:8][C:9]2[C:13]([C:14]([O:16][CH2:17][CH3:18])=[O:15])=[N:12][N:11]([CH3:19])[C:10]=2[C:20]\1=O)C.C(=O)(O)O.[NH2:26][C:27]([NH2:29])=[NH:28]>CCO>[NH2:28][C:27]1[N:29]=[C:20]2[C:10]3[N:11]([CH3:19])[N:12]=[C:13]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[C:9]=3[CH2:8][CH2:7][CH2:6][C:5]2=[CH:4][N:26]=1
CCOC(=O)c1nn(C)c2c1CCC/C(=C\N(C)C)C2=O
N=C(N)N
null
O=C(O)O
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
null
null
To a solution of ethyl (7E)-7-[(dimethylamino)methylidene]-1-methyl-8-oxo-1,4,5,6,7,8-hexahydrocyclohepta[c]pyrazole-3-carboxylate (240 mg, 0.86 mmol) in EtOH (7.5 mL), guanidine carbonate (86 mg, 0.47 mmol) was added. The reaction mixture was stirred under reflux for 24 h. The solvent was removed under reduced pressure, the crude was triturated with hexane and EtOH and collected by filtration to give 84 mg of a white solid (79% yield).
CCOC(=O)c1nn(C)c2c1CCCc1cnc(N)nc1-2
null
62.2
null
1,528,351
ord_dataset-8c74302143c04eb9983e4b3a7ead2d72
null
2014-01-01T00:12:00
true
C[O:2][C:3](=O)[CH:4]=[CH:5][C:6](=[C:11]([NH:13][CH2:14][CH:15]1[CH2:19][CH2:18][CH2:17][CH2:16]1)[CH3:12])[C:7]([O:9][CH3:10])=[O:8].C[O-].[Na+].[Br:24]N1C(=O)CCC1=O>CO>[CH3:10][O:9][C:7]([C:6]1[CH:5]=[C:4]([Br:24])[C:3](=[O:2])[N:13]([CH2:14][CH:15]2[CH2:19][CH2:18][CH2:17][CH2:16]2)[C:11]=1[CH3:12])=[O:8]
COC(=O)C=CC(C(=O)OC)=C(C)NCC1CCCC1
O=C1CCC(=O)N1Br
null
C[O-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
25
null
MeOH (240 mL) was added to a flask containing 4-[1-(cyclopentylmethyl-amino)-ethylidene]-pent-2-enedioic acid dimethyl ester (7.2 g, 25.6 mmol). NaOMe solution (5.9 mL, 25.6 mmol, 4.375 M in MeOH) and N-bromosuccinimide (5.5 g, 30.7 mmol) were added, and the resulting mixture was refluxed for 1 h. After cooling to r.t., the solvent was evaporated in vacuo. Saturated NH4Cl was added, and the resulting mixture was extracted with CH2Cl2. The organic layer was dried over MgSO4 and concentrated. The crude product was chromatographed (0-25% EtOAc/hexanes) to give 4.46 g of the title compound. MS: (+) m/z 350.22, 352.24 (M+Na, 79/81Br).
COC(=O)c1cc(Br)c(=O)n(CC2CCCC2)c1C
null
53.1
null
698,727
ord_dataset-4e9c2fa02a7544fd839206719263345f
null
2006-01-01T00:02:00
true
[N+:1]([C:4]1[CH:25]=[CH:24][C:7]([CH2:8][O:9][C:10](=[O:23])[CH2:11][N:12](C(OC(C)(C)C)=O)[CH:13]([CH3:15])[CH3:14])=[CH:6][CH:5]=1)([O-:3])=[O:2].[ClH:26].C(OCC)C>O1CCOCC1>[ClH:26].[N+:1]([C:4]1[CH:5]=[CH:6][C:7]([CH2:8][O:9][C:10](=[O:23])[CH2:11][NH:12][CH:13]([CH3:14])[CH3:15])=[CH:24][CH:25]=1)([O-:3])=[O:2]
CC(C)N(CC(=O)OCc1ccc([N+](=O)[O-])cc1)C(=O)OC(C)(C)C
null
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCOCC
C1COCCO1
null
null
null
null
null
null
null
null
null
25
8
To a solution of (N-t-butoxycarbonyl-N-isopropyl-amino)-acetic acid p-nitrobenzyl ester (1.93 g, 5.48 mmol) in 1,4-dioxane (20 ml) was added a solution of 4N hydrogen chloride in 1,4-dioxane (20 ml) in an ice bath, and the mixture was stirred at room temperature overnight. After checking the completion of the reaction, diethyl ether was added thereto the reaction mixture was stirred for 30 minutes and filtered, and the obtained residue was washed with diethyl ether and dried to give (isopropylamino)acetic acid p-nitrobenzyl ester hydrochloride (1.50 g, yield 95%) as white crystals.
CC(C)NCC(=O)OCc1ccc([N+](=O)[O-])cc1
null
95
null
214,238
ord_dataset-b67d30cd146f49dcbf24faee022f1a09
null
1990-01-01T00:08:00
true
[NH2:1][C:2]1[N:3]([CH3:13])[C:4]2[C:9]([C:10]=1[C:11]#[N:12])=[CH:8][CH:7]=[CH:6][CH:5]=2.[C:14]([O:20][CH2:21][CH3:22])(=[O:19])[CH2:15][C:16]([CH3:18])=O>>[NH2:12][C:11]1[C:10]2[C:9]3[C:4](=[CH:5][CH:6]=[CH:7][CH:8]=3)[N:3]([CH3:13])[C:2]=2[N:1]=[C:16]([CH3:18])[C:15]=1[C:14]([O:20][CH2:21][CH3:22])=[O:19]
CCOC(=O)CC(C)=O
Cn1c(N)c(C#N)c2ccccc21
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared from 2-amino-1-methyl-1H-indole-3-carbonitrile (D22) and ethyl acetoacetate using a method similar to that described in Description 2.
CCOC(=O)c1c(C)nc2c(c1N)c1ccccc1n2C
null
null
null
1,128,357
ord_dataset-285df12e34cd46e993e3c8ebc3a8962a
null
2012-01-01T00:01:00
true
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH2:8][F:9])[N:3]=1.[C:10]([O:14][C:15](=[O:31])[N:16]([C:23]1[CH:28]=[CH:27][C:26]([F:29])=[CH:25][C:24]=1[CH3:30])[C:17](=[O:22])[CH2:18][CH2:19][C:20]#[CH:21])([CH3:13])([CH3:12])[CH3:11]>>[C:10]([O:14][C:15](=[O:31])[N:16]([C:17](=[O:22])[CH2:18][CH2:19][C:20]#[C:21][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([CH2:8][F:9])[N:3]=1)[C:23]1[CH:28]=[CH:27][C:26]([F:29])=[CH:25][C:24]=1[CH3:30])([CH3:13])([CH3:11])[CH3:12]
C#CCCC(=O)N(C(=O)OC(C)(C)C)c1ccc(F)cc1C
FCc1cccc(Br)n1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
The title compound was prepared in accordance with the general method of Example 1, from 2-bromo-6-(fluoromethyl)pyridine (150 mg, 0.79 nm mmol, Example 190(E)) and (4-fluoro-2-methyl-phenyl)-pent-4-ynoyl-carbamic acid tert-butyl ester (241 mg, 0.79 mmol, 188(B)). Reaction time: 3 hours. The crude residue was purified by flash chromatography (cyclohexane/AcOEt 4:1) to yield 260 mg (0.63 mmol, 790%) of [5-(6-fluoromethyl-pyridin-2-yl)-pent-4-ynoyl]-(4-fluoro-2-methyl-phenyl)-carbamic acid tert-butyl ester as a white solid.
Cc1cc(F)ccc1N(C(=O)CCC#Cc1cccc(CF)n1)C(=O)OC(C)(C)C
null
79.8
null
243,469
ord_dataset-fa3b512e2d924b9b965301ebcba6853d
null
1992-01-01T00:03:00
true
[CH:1]1([NH:4][C:5]2[N:10]=[C:9]([N:11]3[CH2:16][CH2:15][N:14]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH2:13][CH2:12]3)[C:8]([F:22])=[CH:7][CH:6]=2)[CH2:3][CH2:2]1.[CH2:23]([O:25][C:26](=[O:37])[C:27](=[CH:33]OCC)[C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH3:24]>C1(C)C(C)=CC=CC=1>[CH:1]1([N:4]([CH:33]=[C:27]([C:26]([O:25][CH2:23][CH3:24])=[O:37])[C:28]([O:30][CH2:31][CH3:32])=[O:29])[C:5]2[CH:6]=[CH:7][C:8]([F:22])=[C:9]([N:11]3[CH2:16][CH2:15][N:14]([C:17]([O:19][CH2:20][CH3:21])=[O:18])[CH2:13][CH2:12]3)[N:10]=2)[CH2:2][CH2:3]1
CCOC(=O)N1CCN(c2nc(NC3CC3)ccc2F)CC1
CCOC=C(C(=O)OCC)C(=O)OCC
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1C
null
null
null
null
null
null
null
null
null
null
null
null
A solution of 3.8 g (12.3 mmole) of 4-[6-(cyclopropylamino)-3-fluoro-2-pyridinyl]-1-piperazine carboxylic acid, ethyl ester, 2.7 g (12.3 mmole) of diethyl(ethoxymethylene)malonate and 50 ml of xylene was refluxed for 24 hours. The solvent was removed in vacuo and the residue was chromatographed over silica gel eluting with chloroform/ethyl acetate (80/20) to give 2.3 g of the title compound as a viscous oil which was used without further purification.
CCOC(=O)C(=CN(c1ccc(F)c(N2CCN(C(=O)OCC)CC2)n1)C1CC1)C(=O)OCC
null
39.1
null
530,083
ord_dataset-f027aa93238e424fbbf9bad1c7699adc
null
2001-01-01T00:12:00
true
[Cl:1][C:2]1[CH:11]=[C:10]([C:12]([NH:14][CH2:15][C:16]2[C:24]3[N:23]=[CH:22][N:21](C(OC(C)(C)C)=O)[C:20]=3[CH:19]=[CH:18][CH:17]=2)=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([O:6]C)=[O:5]>CO.[OH-].[Li+]>[Cl:1][C:2]1[CH:11]=[C:10]([C:12]([NH:14][CH2:15][C:16]2[C:24]3[NH:23][CH:22]=[N:21][C:20]=3[CH:19]=[CH:18][CH:17]=2)=[O:13])[CH:9]=[CH:8][C:3]=1[C:4]([OH:6])=[O:5]
COC(=O)c1ccc(C(=O)NCc2cccc3c2ncn3C(=O)OC(C)(C)C)cc1Cl
null
null
[Li+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
null
null
null
null
null
null
null
null
null
null
null
A mixture of 4-(azidomethyl)benzimidazole-1-carboxylic acid, 1,1-dimethylethyl ester (Example 13; 1.40, 5.1 mmol), 1-[[3-chloro-4-(methoxycarbonyl)benzoyl]oxy]-2,5-pyrrolidinedione (Example 5; 1.62 g, 5.2 mmol), and 10% palladium on charcoal (210 mg) in methanol (40 mL) and benzene (2 mL) was hydrogenated at atmospheric pressure for 105 min and then filtered through Celite. Tlc indicated that the reaction was not complete so more 10% palladium on charcoal (210 mg) was added and the mixture was hydrogenated at atmospheric pressure for 3 h and then shaken at 50 psi of hydrogen for 3 h. The reaction mixture was allowed to stand under hydrogen for 12 h, then filtered through Celite, evaporated, and chromatographed (20-100% ethyl acetate/hexanes) to give 2-chloro-4-[[[[1-[(1,1-dimethylethoxy)carbonyl]benzimidazol-4-yl]methyl]amino]carbonyl]benzoic acid, methyl ester (1.50 g, 66%). A solution of the ester (1.45 g, 3.3 mmol) in methanol (15 mL) and 3 M lithium hydroxide solution (5.5 mL) was stirred at room temperature overnight. A white solid was filtered off and discarded. The filtrate was evaporated to dryness. Water and 1 M HCl (16.6 mL) were added, and the mixture was filtered and washed with water to give 2-chloro-4-[[[(benzimidazol-4-yl)methyl]amino]carbonyl]-benzoic acid (925 mg, 86%).
O=C(NCc1cccc2nc[nH]c12)c1ccc(C(=O)O)c(Cl)c1
null
85
null
595,913
ord_dataset-843ef38b45484f72826f5f39d8a29c4d
null
2003-01-01T00:06:00
true
[C:1]([CH:4]([CH2:9][CH2:10][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[C:5]([O:7]C)=[O:6])(=[O:3])[CH3:2].[OH-].[Na+]>O1CCOCC1>[C:1]([CH:4]([CH2:9][CH2:10][CH2:11][C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1)[C:5]([OH:7])=[O:6])(=[O:3])[CH3:2]
COC(=O)C(CCCc1ccccc1)C(C)=O
null
null
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
C1COCCO1
null
null
null
null
null
null
null
null
null
null
0
null
1.00 g (4.45 mmol) of methyl 2-acetyl-5-phenylpentanoate is dissolved in 10 ml of dioxane and cooled to 0° C. 8.5 ml of a 1 M sodium hydroxide solution are added with cooling. After a reaction time of 5 h, the batch is concentrated, treated with 10 ml of ethyl acetate and 10 ml of water and extracted by shaking. The water phase is recovered, cooled to 0° C. and slowly treated with 1 N hydrochloric acid with cooling until pH 1 is reached. It is then extracted with dichloromethane. The dichloromethane phase is dried and directly reacted further without concentrating.
CC(=O)C(CCCc1ccccc1)C(=O)O
null
null
null
52,472
ord_dataset-3d470a6df4a04b1996e024a38c53e818
null
1979-01-01T00:03:00
true
[Br:1][C:2]1[CH:3]=[C:4]([CH:11]=[CH:12][CH:13]=1)[C:5]([N:8]=[C:9]=[O:10])([CH3:7])[CH3:6].[C-]#N.[CH3:16][NH:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>>[Br:1][C:2]1[CH:3]=[C:4]([CH:11]=[CH:12][CH:13]=1)[C:5]([NH:8][C:9](=[O:10])[N:17]([CH3:16])[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)([CH3:7])[CH3:6]
CC(C)(N=C=O)c1cccc(Br)c1
CNc1ccccc1
null
[C-]#N
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
60
null
2.4 g of m-bromo-α,α-dimethylbenzyl isocyanate, prepared from the corresponding cyanide in the same way as in Synthesis Example 1, was added to 1.1 g of N-methylaniline and the mixture was heated at 60° C. for 2 hours. After allowing the reaction mixture to cool, the precipitated white crystals were separated by filtration and washed with n-hexane to obtain 3.0 g of the title compound.
CN(C(=O)NC(C)(C)c1cccc(Br)c1)c1ccccc1
null
86.4
null
538,175
ord_dataset-1884c7bf3d544afdb8d17b5d41b90a27
null
2002-01-01T00:03:00
true
[CH:1]([N:4]([CH2:8][C:9]1[CH:41]=[CH:40][C:12]([C:13]([CH:15]2[CH2:20][CH2:19][N:18](C(C3C=CC=CC=3)(C3C=CC=CC=3)C3C=CC=CC=3)[CH2:17][CH2:16]2)=[O:14])=[CH:11][CH:10]=1)[CH:5]([CH3:7])[CH3:6])([CH3:3])[CH3:2]>C(O)(=O)C>[CH:1]([N:4]([CH2:8][C:9]1[CH:10]=[CH:11][C:12]([C:13]([CH:15]2[CH2:20][CH2:19][NH:18][CH2:17][CH2:16]2)=[O:14])=[CH:40][CH:41]=1)[CH:5]([CH3:7])[CH3:6])([CH3:2])[CH3:3]
CC(C)N(Cc1ccc(C(=O)C2CCN(C(c3ccccc3)(c3ccccc3)c3ccccc3)CC2)cc1)C(C)C
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CC(=O)O
null
null
null
null
null
null
null
null
null
null
80
1
A mixture of 4-(4-diisopropylaminomethylbenzoyl)-1-tritylpiperidine (1.3 g) and 80% acetic acid aqueous solution (20 ml) was stirred at 80° C. for 1 hour and concentrated. To the residue was added water, and the solution was extracted with ethyl acetate. The extract was washed with water, dried (MgSO4) and concentrated to give an oil of 4-(4-diisopropylaminomethylbenzoyl)piperidine (1.0 g). To a solution of the oil (302 mg) in THF (10 ml) was added 6-chloronaphthalene-2-sulfonylchloride (261 mg), and the mixture was stirred at room temperature for 1 hour. To the mixture was added sodium hydrogen carbonate aqueous solution, and the mixture was extracted with ethyl acetate. The extract was washed with water, dried (MgSO4) and concentrated. The residue was subjected to silica gel chromatography and eluted with hexane-ethyl acetate (4:1) to give the title compound (0.15g).
CC(C)N(Cc1ccc(C(=O)C2CCNCC2)cc1)C(C)C
null
138.6
null
1,240,449
ord_dataset-c544c0c663f54dbea4ddb52ddde7934e
null
2013-01-01T00:01:00
true
[F:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH:5]=O.C(O)(=O)[CH2:11][C:12]([OH:14])=[O:13].N1CCCCC1.N1C=CC=CC=1.Cl>>[F:1][C:2]1[CH:3]=[C:4]([CH:7]=[CH:8][CH:9]=1)[CH:5]=[CH:11][C:12]([OH:14])=[O:13]
O=Cc1cccc(F)c1
O=C(O)CC(=O)O
null
Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
c1ccncc1
C1CCNCC1
null
null
null
null
null
null
null
null
null
25
1
5 g (40.1 mmol) of 3-fluoro benzaldehyde, 8.38 g (2 eq.) of malonic acid, and 0.34 g (0.1 eq.) of piperidine were added to 9.52 g (3 eq.) of pyridine and stirred at room temperature for about 1 hour. After heating it to 80° C., the mixture was stirred for 12 hours. After the reaction, the resulting solution cooled to room temperature and was slowly added with 1M HCl until it was titrated to about pH 4. The resulting powder was filtered and washed with water, and then dried in a vacuum oven. (Yield: 84%)
O=C(O)C=Cc1cccc(F)c1
null
84
null
1,066,181
ord_dataset-ffbef48837674f39816de887b5dc8bae
null
2011-01-01T00:06:00
true
[CH3:1][C@@:2]1([C:8]([OH:10])=O)[CH2:6][O:5][C:4](=[O:7])[O:3]1.C(Cl)(=O)C([Cl:14])=O.CN(C=O)C>ClCCl>[CH3:1][C@@:2]1([C:8]([Cl:14])=[O:10])[CH2:6][O:5][C:4](=[O:7])[O:3]1
C[C@@]1(C(=O)O)COC(=O)O1
O=C(Cl)C(=O)Cl
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
CN(C)C=O
null
null
null
null
null
null
null
null
null
25
0.17
To a solution of the compound prepared in Example 184 (330 mg) in dichloromethane (11 mL) were added oxalyl chloride (290 μL) and DMF (0.1 mL) and the reaction mixture was stirred at room temperature for 10 minutes. The reaction mixture was concentrated in vacuum condition to give the title compound (2.0 g) having the following physical data as a coarse product. This compound was used for the next reaction without being purified.
C[C@@]1(C(=O)Cl)COC(=O)O1
null
null
null
724,123
ord_dataset-0387783899c642a8b7eb4ba379bcdf5d
null
2006-01-01T00:08:00
true
[Br:1][C:2]1[S:6][C:5]([C:7](=[O:9])C)=[C:4]([CH3:10])[CH:3]=1.[BH4-].[Na+].Cl>C(O)C>[Br:1][C:2]1[S:6][C:5]([CH2:7][OH:9])=[C:4]([CH3:10])[CH:3]=1
CC(=O)c1sc(Br)cc1C
null
null
Cl
[BH4-]
[Na+]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CCO
null
null
null
null
null
null
null
null
null
null
0
1
A mixture of 1-(5-bromo-3-methylthien-2-yl)ethanone (intermediate 82, 5.13 g) in ethanol (50 ml) was treated with sodium borohydride (0.947 g). The reaction was stirred at 0° C. for 60 minutes and warmed to room temp for 30 minutes. 2M Aqueous hydrochloric acid was added and the reaction mixture was extracted with ethyl acetate twice. The organic solutions were combined and dried with brine and over magnesium sulfate. The title compound was isolated after removal of the desiccant and evaporation of the solvent.
Cc1cc(Br)sc1CO
null
null
null
1,391,012
ord_dataset-31641fb65b34430fa7435229b949b604
null
2014-01-01T00:01:00
true
[CH3:1][C:2]1[CH:6]=[C:5]([NH2:7])[N:4]([CH:8]2[CH2:13][CH2:12][N:11]([CH3:14])[CH2:10][CH2:9]2)[N:3]=1.[CH:15]1([C:18](=O)[CH2:19][C:20](=O)[C:21]([O:23][CH2:24][CH3:25])=[O:22])[CH2:17][CH2:16]1>C1(C)C=CC=CC=1>[CH:15]1([C:18]2[CH:19]=[C:20]([C:21]([O:23][CH2:24][CH3:25])=[O:22])[C:6]3[C:2]([CH3:1])=[N:3][N:4]([CH:8]4[CH2:13][CH2:12][N:11]([CH3:14])[CH2:10][CH2:9]4)[C:5]=3[N:7]=2)[CH2:16][CH2:17]1
Cc1cc(N)n(C2CCN(C)CC2)n1
CCOC(=O)C(=O)CC(=O)C1CC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
Cc1ccccc1
null
null
null
null
null
null
null
null
null
null
70
null
3-Methyl-1-(1-methyl-4-piperidinyl)-1H-pyrazol-5-amine (500 mg, 2.57 mmol) and ethyl 4-cyclopropyl-2,4-dioxobutanoate (474 mg, 2.57 mmol) were suspended in Toluene (10 mL) and heated at 70° C. for 5 h. The solvent was removed in vacuo and the crude residue was purified via silica gel chromatography (eluent: gradient of 0 to 10% MeOH:DCM). The final product was collected as a solid, 0.722 g (76%). LCMS E-S (M+H)=343.1 1H NMR (400 MHz, DMSO-d6) δ ppm 1.03-1.11 (m, 4H), 1.38 (t, J=7.07 Hz, 3H), 1.83 (d, J=6.06 Hz, 2H), 2.12-2.22 (m, 4H), 2.27 (s, 3H), 2.35 (m, J=7.83, 7.83, 5.05, 4.80 Hz, 1H), 2.54 (s, 3H), 2.94 (d, J=6.57 Hz, 2H), 4.42 (q, J=7.16 Hz, 2H), 4.57-4.73 (m, 1H), 7.46 (s, 1H).
CCOC(=O)c1cc(C2CC2)nc2c1c(C)nn2C1CCN(C)CC1
null
null
null
922,226
ord_dataset-8e59bd24817446f7b1c68e805b8e5f1d
null
2009-01-01T00:11:00
true
[Cl:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[N:9]1[C:17](=[O:18])[C:16]2[C@H:15]3[C:19]([CH3:21])([CH3:20])[C@:12]([CH3:22])([CH2:13][CH2:14]3)[C:11]=2[NH:10]1.I[CH2:24][CH2:25][CH:26]([CH3:28])[CH3:27]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C)C=O>[Cl:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[N:9]1[C:17](=[O:18])[C:16]2[C@H:15]3[C:19]([CH3:21])([CH3:20])[C@:12]([CH3:22])([CH2:13][CH2:14]3)[C:11]=2[N:10]1[CH2:24][CH2:25][CH:26]([CH3:28])[CH3:27]
CC1(C)[C@H]2CC[C@]1(C)c1[nH]n(-c3ccc(F)cc3Cl)c(=O)c12
CC(C)CCI
null
CCCC[N+](CCCC)(CCCC)CCCC
[I-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CN(C)C=O
null
null
null
null
null
null
null
null
null
null
80
null
A mixture of (4R,7S)-2-(2-chloro-4-fluoro-phenyl)-7,8,8-trimethyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (Intermediate 43; 150 mg, 0.47 mmol), tetrabutylammonium iodide (174 mg, 0.47 mmol) and 1-iodo-3-methylbutane (230 μL, 1.75 mmol) in dimethylformamide (3 mL) was heated at 80° C. for 4 days. The solvent was evaporated and dichloromethane (50 mL) was added. The solution was washed with water (2×20 mL), saturated aqueous sodium thiosulfate (20 mL), and brine (20 mL), dried (magnesium sulfate), filtered, concentrated, purified by chromatography, eluting with 60-80% ethyl acetate/petroleum ether, and dried under high vacuum overnight to give (4R,7S)-2-(2-chloro-4-fluoro-phenyl)-7,8,8-trimethyl-1-(3-methyl-butyl)-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (31 mg, 17%) as a tacky oil. APCI(+)-MS (M+H) 391.
CC(C)CCn1c2c(c(=O)n1-c1ccc(F)cc1Cl)[C@@H]1CC[C@@]2(C)C1(C)C
null
16.9
null
842,883
ord_dataset-e2b35e721c2741999b0005d12691f9fe
null
2008-01-01T00:10:00
true
FC(F)(F)C(O)=O.[CH3:8][O:9][C:10](=[O:32])[C:11]1[CH:16]=[C:15]([O:17]COC)[CH:14]=[C:13]([O:21][C:22]2[CH:27]=[CH:26][C:25]([S:28]([CH3:31])(=[O:30])=[O:29])=[CH:24][CH:23]=2)[CH:12]=1>C(Cl)Cl>[CH3:8][O:9][C:10](=[O:32])[C:11]1[CH:16]=[C:15]([OH:17])[CH:14]=[C:13]([O:21][C:22]2[CH:23]=[CH:24][C:25]([S:28]([CH3:31])(=[O:29])=[O:30])=[CH:26][CH:27]=2)[CH:12]=1
COCOc1cc(Oc2ccc(S(C)(=O)=O)cc2)cc(C(=O)OC)c1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
ClCCl
O=C(O)C(F)(F)F
null
null
null
null
null
null
null
null
null
25
4
After adding 60 ml of trifluoroacetic acid to a solution of 30.9 g (84.3 mmol) of the obtained 3-(4-methanesulfonyl-phenoxy)-5-methoxymethoxy-benzoic acid methyl ester in methylene chloride (100 ml) while cooling on ice, the reaction mixture was stirred at room temperature for 4 hours. The reaction mixture was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (hexane:acetic acid ethyl ester=1:1) to obtain 15.2 g of 5-hydroxy-3-(4-methanesulfonyl-phenoxy)benzoic acid methyl ester (yield: 56%) as a white solid.
COC(=O)c1cc(O)cc(Oc2ccc(S(C)(=O)=O)cc2)c1
null
55.9
null
1,035,407
ord_dataset-3af92aec23dc4810b92eb0d8c60023ee
null
2011-01-01T00:03:00
true
[CH:1]1[C:10]2[C:5](=[CH:6][C:7]([CH:11]=O)=[CH:8][CH:9]=2)[CH:4]=[CH:3][N:2]=1.Cl.[NH2:14][OH:15].[OH-].[Na+].Cl>CCO.O>[CH:1]1[C:10]2[C:5](=[CH:6][C:7](/[CH:11]=[N:14]/[OH:15])=[CH:8][CH:9]=2)[CH:4]=[CH:3][N:2]=1
O=Cc1ccc2cnccc2c1
NO
null
Cl
[Na+]
[OH-]
null
null
null
null
null
null
null
null
null
null
null
null
null
null
O
CCO
null
null
null
null
null
null
null
null
null
0
2
To a solution of isoquinoline-6-carbaldehyde (2.48 g, 15.8 mmol) (prepared as shown in Example 6) in 160 mL of 1:2 EtOH:H2O was added hydroxylamine hydrochloride (1.21 g, 17.4 mmol). The mixture was cooled to 0° C., and 50 wt % NaOH in H2O (3.2 mL, 0.2 mL per mmol of aldehyde) was added dropwise. The mixture was then stirred at 0° C. for 2 hours, at which time the pH was adjusted to about 6 with 10% aqueous HCl. The resulting biphasic mixture was then transferred to a separatory funnel and extracted five times with 150 mL of DCM. The combined organic layers were dried over MgSO4. Concentration under reduced pressure afforded (E)-isoquinoline-6-carbaldehyde oxime (2.14 g, 78.8% yield) as a white solid. 1H NMR (400 MHz, CD3OD) δ ppm 9.20 (s, 1H), 8.44 (d, J=5.9 Hz, 1H), 8.28 (s, 1H), 8.06 (s, 2H), 7.99 (s, 1H), 7.83 (s, 5.9 Hz, 1H).
O/N=C/c1ccc2cnccc2c1
null
78.7
null
336,871
ord_dataset-65c44df6676d4ce3a1874db5d7958ca9
null
1996-01-01T00:08:00
true
Cl[CH2:2][CH2:3][C:4]1[C:5](=[O:23])[O:6][C:7]2[CH:14]=[C:13]([O:15][CH2:16][CH2:17][CH3:18])[CH:12]=[C:11]([O:19][CH2:20][CH2:21][CH3:22])[C:8]=2[C:9]=1[CH3:10].[CH3:24][O:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1[N:32]1[CH2:37][CH2:36][NH:35][CH2:34][CH2:33]1>>[CH3:24][O:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1[N:32]1[CH2:37][CH2:36][N:35]([CH2:2][CH2:3][C:4]2[C:5](=[O:23])[O:6][C:7]3[CH:14]=[C:13]([O:15][CH2:16][CH2:17][CH3:18])[CH:12]=[C:11]([O:19][CH2:20][CH2:21][CH3:22])[C:8]=3[C:9]=2[CH3:10])[CH2:34][CH2:33]1
CCCOc1cc(OCCC)c2c(C)c(CCCl)c(=O)oc2c1
COc1ccccc1N1CCNCC1
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
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Process B; starting materials: 3-(2-chloroethyl)-4-methyl-5,7-dipropoxy-2H-1-benzopyran-2-one (Example 38) and 1-(2-methoxyphenyl)piperazine; yield 47% of crude product.
CCCOc1cc(OCCC)c2c(C)c(CCN3CCN(c4ccccc4OC)CC3)c(=O)oc2c1
null
47
null
603,479
ord_dataset-273fda773e864aaf9b71a30a2d9f2162
null
2003-01-01T00:08:00
true
[CH3:1]C(N(C)C)=O.[NH2:7][C:8]1[C:9]([OH:27])=[C:10]([N:16]2[C:21](=[O:22])[N:20]([CH3:23])[C:19](=[S:24])[N:18]([CH3:25])[C:17]2=[O:26])[C:11]([F:15])=[CH:12][C:13]=1[Cl:14]>CO>[Cl:14][C:13]1[C:8]2[N:7]=[CH:1][O:27][C:9]=2[C:10]([N:16]2[C:21](=[O:22])[N:20]([CH3:23])[C:19](=[S:24])[N:18]([CH3:25])[C:17]2=[O:26])=[C:11]([F:15])[CH:12]=1
CC(=O)N(C)C
Cn1c(=S)n(C)c(=O)n(-c2c(F)cc(Cl)c(N)c2O)c1=O
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null
null
null
null
null
null
null
null
null
null
null
null
null
null
null
CO
null
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null
5.0 g (48.1 mmol) of trimethylformamide were added dropwise to a solution of 502 mg (1.50 mmol) of 3-(3-amino-4-chloro-6-fluoro-2-hydroxyphenyl)-1,5-dimethyl-6-thioxo-[1,3,5]-triazinane-2,4-dione in 10 ml of methanol. The mixture was then heated at reflux temperature for 9 hours. The reaction mixture was subsequently concentrated under reduced pressure. The resulting crude product was purified by means of column chromatography (mobile phase: cyclohexane/ethyl acetate=20:1). Yield: 240 mg (46%); m.p.: 209-211° C.
Cn1c(=S)n(C)c(=O)n(-c2c(F)cc(Cl)c3ncoc23)c1=O
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null
null